Block composites in thermoplastic vulcanizate applications

ABSTRACT

Embodiments of the invention provide block composites and their use in thermoplastic vulcanizate compounds.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application claims priority from U.S. Provisional Application Ser.No. 61/248,147, filed Oct. 2, 2009. This application is also related tothe following U.S. Provisional Patent Applications also filed Oct. 2,2009 with Ser. Nos. 61/248,160; and 61/248,170. For purposes of UnitedStates patent practice, the contents of these applications are hereinincorporated by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to block composites and their use inthermoplastic vulcanizates.

BACKGROUND OF THE INVENTION

Elastomers are defined as materials which experience large reversibledeformations under relatively low stress Some examples of commerciallyavailable elastomers include natural rubber, ethylene/propylene (EPM)copolymers, ethylene/propylene/diene (EPDM) copolymers,styrene/butadiene copolymers, chlorinated polyethylene, and siliconerubber.

Thermoplastic elastomers are elastomers having thermoplastic properties.That is, thermoplastic elastomers are optionally molded or otherwiseshaped and reprocessed at temperatures above their melting or softeningpoint. One example of a thermoplastic elastomer isstyrene-butadiene-styrene (SBS) block copolymer. SBS block copolymersexhibit a two phase morphology consisting of glassy polystyrene domainsconnected by rubbery butadiene segments.

Thermoset elastomers are elastomers having thermoset properties. Thatis, thermoset elastomers irreversibly solidify or “set” when heated,generally due to an irreversible crosslinking reaction. Two examples ofthermoset elastomers are crosslinked ethylene-propylene monomer rubber(EPM) and crosslinked ethylene-propylene-diene monomer rubber (EPDM).EPM materials are made by copolymerization of ethylene and propylene.EPM materials are typically cured with peroxides to give rise tocrosslinking, and thereby induce thermoset properties. EPDM materialsare linear interpolymers of ethylene, propylene, and a nonconjugateddiene such as 1,4-hexadiene, dicyclopentadiene, or ethylidenenorbornene. EPDM materials are typically vulcanized with sulfur toinduce thermoset properties, although they also can be cured withperoxides. While EPM and EPDM thermoset materials are advantageous inthat they have applicability in higher temperature applications, EPM andEPDM elastomers have relatively low green strength (at lower ethylenecontents), relatively low oil resistance, and relatively low resistanceto surface modification.

Thermoplastic vulcanizates (TPV's) comprises thermoplastic matrices,preferably crystalline, through which thermoset elastomers are generallyuniformly distributed. Examples of thermoplastic vulcanizates includeethylene-propylene monomer rubber and ethylene-propylene-diene monomerrubber thermoset materials distributed in a crystalline polypropylenematrix. One example of a commercial TPV is Satoprene® thermoplasticrubber which is manufactured by Advanced Elastomer Systems and is amixture of crosslinked EPDM particles in a crystalline polypropylenematrix. These materials have found utility in many applications whichpreviously used vulcanized rubber, e.g., hoses, gaskets, and the like.

Commercial TPVs are typically based on vulcanized rubbers in which aphenolic resin or sulfur cure system is used to vulcanize, that is tocrosslink, a diene (or more generally, a polyene) copolymer rubber byway of dynamic vulcanization, that is crosslinking while mixing(typically vigorously), in a thermoplastic matrix.

Although numerous types of thermoplastic vulcanizates are known, thereis still a need for improved thermoplastic materials having elastomericproperties. Specifically, there is a need for a method to producethermoplastic vulcanizates having improved tensile properties,elongation, compression set, and/or oil resistance.

SUMMARY OF THE INVENTION

Thermoplastic vulcanizates have now been discovered that have improvedelastomeric properties, particularly improved compression set atelevated temperatures. These new thermoplastic vulcanizates are obtainedfrom a reaction mixture comprising:

-   -   (i) a thermoplastic polyolefin    -   (ii) a vulcanizable elastomer    -   (iii) a crosslinking agent; and,    -   (iv) a block composite.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the DSC melting curve for Example B1.

FIG. 2 shows the DSC melting curve for Example F1.

FIG. 3 compares the TREF profiles of Examples B1, C1 and D1.

FIG. 4 shows DSC curves of Examples B2 and B3.

FIG. 5 shows DSC curves of Examples F2 and F3.

FIG. 6 shows Block Composite Index for Examples B1, F1, C1, H1, D1 andG1.

FIG. 7 shows Block Composite Index for Examples B1, V1, Z1, C1, W1, AA1,D1, X1, and AB1.

FIG. 8 shows Dynamic Mechanical Analysis of Examples B1, C1 and D1.

FIG. 9 shows Dynamic Mechanical Analysis of Examples F1, G1 and H1.

FIG. 10 shows a TEM Micrograph of Profax Ultra SG853 PolypropyleneImpact Copolymer at 5 μm and 1 μm scales.

FIG. 11 shows TEM Micrographs of Examples B1, C1 and D1 at 2 μm, 1 μmand 0.5 μm scales.

FIG. 12 shows TEM Micrographs of Examples F1, G1 and H1 at 2 μm, 1 μmand 0.5 μm scales.

FIG. 13 shows TEM micrographs of Examples B2, D2 and B3 at 0.5 μm and0.2 μm scales.

FIG. 14 shows Example B2 at 1 μm and 200 nm scales.

FIG. 15 shows AFM images of Comparative Example T1 on the left andExample T4 on the right.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Definitions

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Group or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference)especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

The term “comprising” and derivatives thereof is not intended to excludethe presence of any additional component, step or procedure, whether ornot the same is disclosed herein. In order to avoid any doubt, allcompositions claimed herein through use of the term “comprising” mayinclude any additional additive, adjuvant, or compound whether polymericor otherwise, unless stated to the contrary. In contrast, the term,“consisting essentially of” excludes from the scope of any succeedingrecitation any other component, step or procedure, excepting those thatare not essential to operability. The term “consisting of” excludes anycomponent, step or procedure not specifically delineated or listed. Theterm “or”, unless stated otherwise, refers to the listed membersindividually as well as in any combination.

The term “polymer”, includes both conventional homopolymers, that is,homogeneous polymers prepared from a single monomer, and copolymers(interchangeably referred to herein as interpolymers), meaning polymersprepared by reaction of at least two monomers or otherwise containingchemically differentiated segments or blocks therein even if formed froma single monomer. More specifically, the term “polyethylene” includeshomopolymers of ethylene and copolymers of ethylene and one or more C₃₋₈α-olefins in which ethylene comprises at least 50 mole percent. The term“propylene copolymer” or “propylene interpolymer” means a copolymercomprising propylene and one or more copolymerizable comonomers, whereina plurality of the polymerized monomer units of at least one block orsegment in the polymer (the crystalline block) comprise propylene,preferably at least 90 mole percent, more preferably at least 95 molepercent, and most preferably at least 98 mole percent. A polymer madeprimarily from a different α-olefin, such as 4-methyl-1-pentene would benamed similarly. The term “crystalline” if employed, refers to a polymeror polymer block that possesses a first order transition or crystallinemelting point (Tm) as determined by differential scanning calorimetry(DSC) or equivalent technique. The term may be used interchangeably withthe term “semicrystalline”. The term “amorphous” refers to a polymerlacking a crystalline melting point. The term, “isotactic” is defined aspolymer repeat units having at least 70 percent isotactic pentads asdetermined by ¹³C-NMR analysis. “Highly isotactic” is defined aspolymers having at least 90 percent isotactic pentads.

The term “block copolymer” or “segmented copolymer” refers to a polymercomprising two or more chemically distinct regions or segments (referredto as “blocks”) preferably joined in a linear manner, that is, a polymercomprising chemically differentiated units which are joined end-to-endwith respect to polymerized ethylenic functionality, rather than inpendent or grafted fashion. In a preferred embodiment, the blocks differin the amount or type of comonomer incorporated therein, the density,the amount of crystallinity, the crystallite size attributable to apolymer of such composition, the type or degree of tacticity (isotacticor syndiotactic), regio-regularity or regio-irregularity, the amount ofbranching, including long chain branching or hyper-branching, thehomogeneity, or any other chemical or physical property. The blockcopolymers of the invention are characterized by unique distributions ofboth polymer polydispersity (PDI or Mw/Mn), block length distribution,and/or block number distribution, due, in a preferred embodiment, to theeffect of the shuttling agent(s) in combination with the catalyst(s).

The term “block composite” refers to the novel polymers of the inventioncomprising a soft copolymer, a hard polymer and a block copolymer havinga soft segment and a hard segment, wherein the hard segment of the blockcopolymer is the same composition as the hard polymer in the blockcomposite and the soft segment of the block copolymer is the samecomposition as the soft copolymer of the block composite. The blockcopolymers can be linear or branched. More specifically, when producedin a continuous process, the block composites desirably possess PDI from1.7 to 15, preferably from 1.8 to 3.5, more preferably from 1.8 to 2.2,and most preferably from 1.8 to 2.1. When produced in a batch orsemi-batch process, the block composites desirably possess PDI from 1.0to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, andmost preferably from 1.4 to 1.8.

“Hard” segments refer to highly crystalline blocks of polymerized unitsin which the monomer is present in an amount greater than 95 weightpercent, and preferably greater than 98 weight percent. In other words,the comonomer content in the hard segments is less than 5 weightpercent, and preferably less than 2 weight percent. In some embodiments,the hard segments comprise all or substantially all propylene units.“Soft” segments, on the other hand, refer to amorphous, substantiallyamorphous or elastomeric blocks of polymerized units in which thecomonomer content is greater than 10 mol %.

The term “thermoplastic vulcanizate” (TPV) refers to an engineeringthermoplastic elastomer in which a cured elastomeric phase is dispersedin a thermoplastic matrix. It typically comprises at least onethermoplastic material and at least one cured (i.e., cross-linked)elastomeric material. Preferably, the thermoplastic material forms thecontinuous phase, and the cured elastomer forms the discrete phase; thatis, domains of the cured elastomer are dispersed in the thermoplasticmatrix. Preferably, the domains of the cured elastomer are fully anduniformly dispersed with the average domain size in the range from about0.1 micron to about 100 micron, from about 0.1 micron to about 50microns; from about 0.1 micron to about 25 microns; from about 0.1micron to about 10 microns, or from about 0.11 micron to about 5microns. In some embodiments, the matrix phase of the TPV is present byless than about 50% by volume of the TPV, and the dispersed phase ispresent by at least about 50% by volume of the TPV. In other words, thecrosslinked elastomeric phase is the major phase in the TPV, whereas thethermoplastic polymer is the minor phase. TPVs with such phasecomposition have good compression set. However, TPVs with the majorphase being the thermoplastic polymer and the minor phase being thecross-linked elastomer may also be made. Generally, the cured elastomerhas a portion that is insoluble in cyclohexane at 23° C. The amount ofthe insoluble portion is preferably more than about 75% or about 85%. Insome cases, the insoluble amount is more than about 90%, more than about93%, more than about 95% or more than about 97% by weight of the totalelastomer.

The branching index quantifies the degree of long chain branching in aselected thermoplastic polymer. Preferably, the branching index is lessthan about 0.9, 0.8, 0.7, 0.6 or 0.5. In some embodiments, the branchingindex is in the range from about 0.01 to about 0.4. In otherembodiments, the branching index is less than about 0.01, less thanabout 0.001, less than about 0.0001, less than about 0.00001, or lessthan about 0.000001. It is defined by the following equation:

${{g^{\prime} = \frac{{IV}_{Br}}{{IV}_{Lin}}}}_{M_{w}}$where g′ is the branching index, IV_(Br) is the intrinsic viscosity ofthe branched thermoplastic polymer (e.g., polypropylene) and IV_(Lin) isthe intrinsic viscosity of the corresponding linear thermoplasticpolymer having the same weight average molecular weight as the branchedthermoplastic polymer and, in the case of copolymers and terpolymers,substantially the same relative molecular proportion or proportions ofmonomer units.

Intrinsic viscosity, also known as the limiting viscosity number, in itsmost general sense is a measure of the capacity of a polymer molecule toenhance the viscosity of a solution. This depends on both the size andthe shape of the dissolved polymer molecule. Hence, in comparing anonlinear polymer with a linear polymer of substantially the same weightaverage molecular weight, it is an indication of configuration of thenonlinear polymer molecule. Indeed, the above ratio of intrinsicviscosities is a measure of the degree of branching of the nonlinearpolymer. A method for determining intrinsic viscosity of propylenepolymer material is described by Elliott et al., J. App. Poly. Sci., 14,pp 2947-2963 (1970). In this specification the intrinsic viscosity ineach instance is determined with the polymer dissolved indecahydronaphthalene at 135.degree. C. Another method for measuring theintrinsic viscosity of a polymer is ASTM D5225-98—Standard Test Methodfor Measuring Solution Viscosity of Polymers with a DifferentialViscometer, which is incorporated by reference herein in its entirety.

Embodiments of the invention provide a kind of thermoplastic vulcanizate(TPV) composition and a process for making various TPVs. Such TPVs mayhave a lower compression set, lower tensile set, higher tensilestrength, elongation, tear strength, abrasion resistance, better dynamicproperties and/or oil resistance. First, a typical thermoplasticvulcanizate composition comprises a mixture or reaction product of (1) athermoplastic polymer; (2) a vulcanizable elastomer; and (3) across-linking agent capable of vulcanizing the elastomer. Preferably,the cross-linking agent does not substantially degrade or cross-link thethermoplastic polymer. Alternatively, the thermoplastic vulcanizatecomposition of the invention comprises a mixture or reaction product of(1) a thermoplastic polymer; (2) a vulcanizable elastomer; (3) acompatibilizer; and (4) a cross-linking agent capable of vulcanizing theelastomer, wherein the block composites in any chemical form are used asa compatibilizer between the thermoplastic polymer and the vulcanizableelastomer. When used as compatibilizer, the block composite is presentin the TPV by less than 50 percent but greater than zero percent byweight of the total composition. Preferably, the block composite ispresent in an amount of less than 40 percent but greater than zeropercent by weight, less than 30 percent but greater than zero percent byweight, less than 20 percent but greater than zero percent by weight,less than 10 percent but greater than zero percent by weight, less than8 percent by weight but greater than zero percent, less than 6 percentbut greater than zero percent by weight, or less than 5 percent butgreater than zero percent by weight.

The block composite polymers of the invention are preferably prepared bya process comprising contacting an addition polymerizable monomer ormixture of monomers under addition polymerization conditions with acomposition comprising at least one addition polymerization catalyst, acocatalyst and a chain shuttling agent, said process being characterizedby formation of at least some of the growing polymer chains underdifferentiated process conditions in two or more reactors operatingunder steady state polymerization conditions or in two or more zones ofa reactor operating under plug flow polymerization conditions.

In a preferred embodiment, the block composites of the inventioncomprise a fraction of block polymer which possesses a most probabledistribution of block lengths. Preferred polymers according to theinvention are block copolymers containing 2 or 3 blocks or segments. Ina polymer containing three or more segments (that is blocks separated bya distinguishable block) each block may be the same or chemicallydifferent and generally characterized by a distribution of properties.In a process for making the polymers, chain shuttling is used as a wayto prolong the lifetime of a polymer chain such that a substantialfraction of the polymer chains exit at least the first reactor of amultiple reactor series or the first reactor zone in a multiple zonedreactor operating substantially under plug flow conditions in the formof polymer terminated with a chain shuttling agent, and the polymerchain experiences different polymerization conditions in the nextreactor or polymerization zone. Different polymerization conditions inthe respective reactors or zones include the use of different monomers,comonomers, or monomer/comonomer(s) ratio, different polymerizationtemperatures, pressures or partial pressures of various monomers,different catalysts, differing monomer gradients, or any otherdifference leading to formation of a distinguishable polymer segment.Thus, at least a portion of the polymer comprises two, three, or more,preferably two or three, differentiated polymer segments arrangedintramolecularly.

The following mathematical treatment of the resulting polymers is basedon theoretically derived parameters that are believed to apply anddemonstrate that, especially in two or more steady-state, continuousreactors or zones connected in series, having differing polymerizationconditions to which the growing polymer is exposed, the block lengths ofthe polymer being formed in each reactor or zone will conform to a mostprobable distribution, derived in the following manner, wherein pi isthe probability of polymer propagation in a reactor with respect toblock sequences from catalyst i. The theoretical treatment is based onstandard assumptions and methods known in the art and used in predictingthe effects of polymerization kinetics on molecular architecture,including the use of mass action reaction rate expressions that are notaffected by chain or block lengths, and the assumption that polymerchain growth is completed in a very short time compared to the meanreactor residence time. Such methods have been previously disclosed inW. H. Ray, J. Macromol. Sci., Rev. Macromol. Chem., C8, 1 (1972) and A.E. Hamielec and J. F. MacGregor, “Polymer Reaction Engineering”, K. H.Reichert and W. Geisler, Eds., Hanser, Munich, 1983. In addition, it isassumed that each incidence of the chain shuttling reaction in a givenreactor results in the formation of a single polymer block, whereastransfer of the chain shuttling agent terminated polymer to a differentreactor or zone and exposure to different polymerization conditionsresults in formation of a different block. For catalyst i, the fractionof sequences of length n being produced in a reactor is given by Xi[n],where n is an integer from 1 to infinity representing the total numberof monomer units in the block.

Xi[n] = (1 − pi)pi(n − 1)  most  probable  distribution  of  block  lengths${Ni} = {\frac{1}{1 - {pi}}\mspace{14mu}{number}\mspace{14mu}{average}\mspace{14mu}{block}\mspace{14mu}{length}}$

If more than one catalyst is present in a reactor or zone, each catalysthas a probability of propagation (pi) and therefore has a unique averageblock length and distribution for polymer being made in that reactor orzone. In a most preferred embodiment the probability of propagation isdefined as:

${{pi} = {{\frac{{Rp}\lbrack i\rbrack}{{{Rp}\lbrack i\rbrack} + {{Rt}\lbrack i\rbrack} + {{Rs}\lbrack i\rbrack} + \lbrack{Ci}\rbrack}\mspace{14mu}{for}\mspace{14mu}{each}\mspace{14mu}{catalyst}\mspace{14mu} i} = \left\{ {1,{2\mspace{14mu}\ldots}}\mspace{14mu} \right\}}},{where},$

-   Rp[i]=Local rate of monomer consumption by catalyst i,    (moles/L/time),-   Rt[i]=Total rate of chain transfer and termination for catalyst i,    (moles/L/time), and-   Rs[i]=Local rate of chain shuttling with dormant polymer,    (moles/L/time).

For a given reactor the polymer propagation rate, Rp[i], is definedusing an apparent rate constant, kpi, multiplied by a total monomerconcentration, [M], and multiplied by the local concentration ofcatalyst i, [Ci], as follows:Rp[i]= kpi[M][Ci]

The chain transfer, termination, and shuttling rate is determined as afunction of chain transfer to hydrogen (H2), beta hydride elimination,and chain transfer to chain shuttling agent (CSA). The quantities [H2]and [CSA] are molar concentrations and each subscripted k value is arate constant for the reactor or zone:Rt[i]=kH2i[H2][Ci]+kβi[Ci]+kai[CSA][Ci]

Dormant polymer chains are created when a polymer moiety transfers to aCSA and all CSA moieties that react are assumed to each be paired with adormant polymer chain. The rate of chain shuttling of dormant polymerwith catalyst i is given as follows, where [CSAf] is the feedconcentration of CSA, and the quantity ([CSAf]−[CSA]) represents theconcentration of dormant polymer chains:Rs[i]=kai[Ci]([CSAf]−[CSA])

As a result of the foregoing theoretical treatment, it may be seen thatthe overall block length distribution for each block of the resultingblock copolymer is a sum of the block length distribution givenpreviously by Xi[n], weighted by the local polymer production rate forcatalyst i. This means that a polymer made under at least two differentpolymer forming conditions will have at least two distinguishable blocksor segments each possessing a most probable block length distribution.

Monomers

Suitable monomers for use in preparing the copolymers of the presentinvention include any addition polymerizable monomer, preferably anyolefin or diolefin monomer, more preferably any α-olefin, and mostpreferably ethylene and at least one copolymerizable comonomer,propylene and at least one copolymerizable comonomer having from 4 to 20carbons, or 1-butene and at least one copolymerizable comonomer having 2or from 5 to 20 carbons, or 4-methyl-1-pentene and at least onedifferent copolymerizable comonomer having from 4 to 20 carbons.Preferably, the copolymers comprise propylene and ethylene. Examples ofsuitable monomers include straight-chain or branched α-olefins of 2 to30, preferably 2 to 20 carbon atoms, such as ethylene, propylene,1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene and 1-eicosene; cycloolefins of 3 to 30,preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene,norbornene, 5-methyl-2-norbornene, tetracyclododecene, and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; di-and poly-olefins, such as butadiene, isoprene, 4-methyl-1,3-pentadiene,1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene,1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene,dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene;aromatic vinyl compounds such as mono- or poly-alkylstyrenes (includingstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene),and functional group-containing derivatives, such as methoxystyrene,ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, o-chlorostyrene, p-chloro styrene,divinylbenzene, 3-phenylpropene, 4-phenylpropene and α-methylstyrene,vinylchloride, 1,2-difluoroethylene, 1,2-dichloroethylene,tetrafluoroethylene, and 3,3,3-trifluoro-1-propene, provided the monomeris polymerizable under the conditions employed.

Preferred monomers or mixtures of monomers for use in combination withat least one CSA herein include ethylene; propylene; mixtures ofethylene with one or more monomers selected from the group consisting ofpropylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, andstyrene; and mixtures of ethylene, propylene and a conjugated ornon-conjugated diene.

Catalysts and Chain Shuttling Agents

Suitable catalysts and catalyst precursors for use in the presentinvention include metal complexes such as disclosed in WO2005/090426, inparticular, those disclosed starting on page 20, line 30 through page53, line 20, which is herein incorporated by reference. Suitablecatalysts are also disclosed in US 2006/0199930; US 2007/0167578; US2008/0311812; U.S. Pat. No. 7,355,089 B2; or WO 2009/012215, which areherein incorporated by reference with respect to catalysts.

Particularly preferred catalysts are those of the following formula:

where:

R²⁰ is an aromatic or inertly substituted aromatic group containing from5 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof;

T³ is a hydrocarbylene or silane group having from 1 to 20 atoms notcounting hydrogen, or an inertly substituted derivative thereof;

M³ is a Group 4 metal, preferably zirconium or hafnium;

G is an anionic, neutral or dianionic ligand group; preferably a halide,hydrocarbyl or dihydrocarbylamide group having up to 20 atoms notcounting hydrogen;

g is a number from 1 to 5 indicating the number of such G groups; and

l bonds and electron donative interactions are represented by lines andarrows respectively.

Preferably, such complexes correspond to the formula:

wherein: T³ is a divalent bridging group of from 2 to 20 atoms notcounting hydrogen, preferably a substituted or unsubstituted, C₃₋₆alkylene group; and

Ar² independently each occurrence is an arylene or an alkyl- oraryl-substituted arylene group of from 6 to 20 atoms not countinghydrogen;

M³ is a Group 4 metal, preferably hafnium or zirconium;

G independently each occurrence is an anionic, neutral or dianionicligand group;

g is a number from 1 to 5 indicating the number of such X groups; and

electron donative interactions are represented by arrows.

Preferred examples of metal complexes of foregoing formula include thefollowing compounds:

where M³ is Hf or Zr;

Ar⁴ is C₆₋₂₀ aryl or inertly substituted derivatives thereof, especially3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl, and

T⁴ independently each occurrence comprises a C₃₋₆ alkylene group, a C₃₋₆cycloalkylene group, or an inertly substituted derivative thereof;

R²¹ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atomsnot counting hydrogen; and

G, independently each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2G groups together are a divalent derivative of the foregoing hydrocarbylor trihydrocarbylsilyl groups.

Especially preferred are compounds of the formula:

wherein Ar⁴ is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,

R²¹ is hydrogen, halo, or C₁₋₄ alkyl, especially methyl

T⁴ is propan-1,3-diyl or butan-1,4-diyl, and

G is chloro, methyl or benzyl.

Other suitable metal complexes are those of the formula:

The foregoing polyvalent Lewis base complexes are conveniently preparedby standard metallation and ligand exchange procedures involving asource of the Group 4 metal and the neutral polyfunctional ligandsource. In addition, the complexes may also be prepared by means of anamide elimination and hydrocarbylation process starting from thecorresponding Group 4 metal tetraamide and a hydrocarbylating agent,such as trimethylaluminum. Other techniques may be used as well. Thesecomplexes are known from the disclosures of, among others, U.S. Pat.Nos. 6,320,005, 6,103,657, and 6,953,764 and International PublicationNos WO 02/38628, and WO 03/40195.

Suitable co-catalysts are those disclosed in WO2005/090426, inparticular, those disclosed on page 54, line 1 to page 60, line 12,which is herein incorporated by reference.

Suitable chain shuttling agents are those disclosed in WO2005/090426, inparticular, those disclosed on page 19, line 21 through page 20 line 12,which is herein incorporated by reference. Particularly preferred chainshuttling agents are dialkyl zinc compounds.

Block Composite Polymer Product

Utilizing the present process, novel block composite polymers arereadily prepared. Preferably, the block composite polymers comprisepropylene, 1-butene or 4-methyl-1-pentene and one or more comonomers.Preferably, the block polymers of the block composites comprise inpolymerized form propylene and ethylene and/or one or more C₄₋₂₀α-olefin comonomers, and/or one or more additional copolymerizablecomonomers or they comprise 4-methyl-1-pentene and ethylene and/or oneor more C₄₋₂₀ α-olefin comonomers, or they comprise 1-butene andethylene, propylene and/or one or more C₅-C₂₀ α-olefin comonomers and/orone or more additional copolymerizable comonomers. Additional suitablecomonomers are selected from diolefins, cyclic olefins, and cyclicdiolefins, halogenated vinyl compounds, and vinylidene aromaticcompounds.

Comonomer content in the resulting block composite polymers may bemeasured using any suitable technique, with techniques based on nuclearmagnetic resonance (NMR) spectroscopy preferred. It is highly desirablethat some or all of the polymer blocks comprise amorphous or relativelyamorphous polymers such as copolymers of propylene, 1-butene or4-methyl-1-pentene and a comonomer, especially random copolymers ofpropylene, 1-butene or 4-methyl-1-pentene with ethylene, and anyremaining polymer blocks (hard segments), if any, predominantly comprisepropylene, 1-butene or 4-methyl-1-pentene in polymerized form.Preferably such segments are highly crystalline or stereospecificpolypropylene, polybutene or poly-4-methyl-1-pentene, especiallyisotactic homopolymers.

Further preferably, the block copolymers of the invention comprise from10 to 90 percent crystalline or relatively hard segments and 90 to 10percent amorphous or relatively amorphous segments (soft segments).Within the soft segments, the mole percent comonomer may range from 5 to90 mole percent, preferably from 10 to 60 mole percent. In the casewherein the comonomer is ethylene, it is preferably present in an amountof 10 wt % to 75 wt %, more preferably from 30 wt % to 70 wt %.

Preferably, the copolymers comprise hard segments that are 80 wt % to100 wt % propylene. The hard segments can be greater than 90 wt %,preferably greater than 95 wt % and more preferably greater than 98 wt %propylene.

The block composite polymers of the invention may be differentiated fromconventional, random copolymers, physical blends of polymers, and blockcopolymers prepared via sequential monomer addition. The blockcomposites may be differentiated from random copolymers bycharacteristics such as higher melting temperatures for a comparableamount of comonomer, block composite index, as described below; from aphysical blend by characteristics such as block composite index, bettertensile strength, improved fracture strength, finer morphology, improvedoptics, and greater impact strength at lower temperature; from blockcopolymers prepared by sequential monomer addition by molecular weightdistribution, rheology, shear thinning, rheology ratio, and in thatthere is block polydispersity.

In some embodiments, the block composites of the invention have a BlockComposite Index (BCI), as defined below, that is greater than zero butless than about 0.4 or from about 0.1 to about 0.3. In otherembodiments, BCI is greater than about 0.4 and up to about 1.0.Additionally, the BCI can be in the range of from about 0.4 to about0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9. Insome embodiments, BCI is in the range of from about 0.3 to about 0.9,from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about0.3 to about 0.6, from about 0.3 to about 0.5, or from about 0.3 toabout 0.4. In other embodiments, BCI is in the range of from about 0.4to about 1.0, from about 0.5 to about 1.0, or from about 0.6 to about1.0, from about 0.7 to about 1.0, from about 0.8 to about 1.0, or fromabout 0.9 to about 1.0.

The block composites preferably have a Tm greater than 100° C.,preferably greater than 120° C., and more preferably greater than 125°C. Preferably the MFR (230° C., 2.16 kg) of the block composite is from0.1 to 1000 dg/min, more preferably from 0.1 to 50 dg/min and morepreferably from 0.1 to 30 dg/min and may also be 1 to 10 dg/min.

Other desirable compositions according to the present invention areelastomeric block copolymers of propylene, 1-butene or4-methyl-1-pentene with ethylene, and optionally one or more α-olefinsor diene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to isobutylene,1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene (when copolymerizedwith propylene), and 1-octene. Suitable dienes for use in preparing suchpolymers, especially multi-block EPDM type polymers include conjugatedor non-conjugated, straight or branched chain-, cyclic- orpolycyclic-dienes containing from 4 to 20 carbons. Preferred dienesinclude 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene,dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene. Aparticularly preferred diene is 5-ethylidene-2-norbornene. The resultingproduct may comprise isotactic homopolymer segments alternating withelastomeric copolymer segments, made in situ during the polymerization.Preferably, the product may be comprised solely of the elastomeric blockcopolymer of propylene, 1-butene or 4-methyl-1-pentene with one or morecomonomers, especially ethylene.

Because the diene containing polymers contain alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

Further preferably, the block composites of this embodiment of theinvention have a weight average molecular weight (Mw) from 10,000 toabout 2,500,000, preferably from 35000 to about 1,000,000 and morepreferably from 50,000 to about 300,000, preferably from 50,000 to about200,000.

The polymers of the invention may be oil extended with from 5 to about95 percent, preferably from 10 to 60 percent, more preferably from 20 to50 percent, based on total composition weight, of a processing oil.Suitable oils include any oil that is conventionally used inmanufacturing extended EPDM rubber formulations. Examples include bothnaphthenic- and paraffinic-oils, with paraffinic oils being preferred.

Any cross-linking agent which is capable of curing an EPDM can be usedin embodiments of the invention. Suitable curing agents include, but arenot limited to, phenolic resin, peroxides, azides, aldehyde-aminereaction products, vinyl silane grafted moieties, hydrosilylation,substituted ureas, substituted guanidines; substituted xanthates;substituted dithiocarbamates; sulfur-containing compounds, such asthiazoles, imidazoles, sulfenamides, thiuramidisulfides,paraquinonedioxime, dibenzoparaquinonedioxime, sulfur; and combinationsthereof. Suitable cross-linking agents may also be used such as thosedisclosed in U.S. Pat. No. 7,579,408, col. 31, line 54 through col. 34,line 52, which disclosure is herein incorporated by reference.

An elastomer composition according to this embodiment of the inventionmay include carbon black. Preferably, the carbon black is present in theamount of from 10 to 80 percent, more preferably from 20 to 60 percent,based on total composition weight.

Additional components of the present formulations usefully employedaccording to the present invention include various other ingredients inamounts that do not detract from the properties of the resultantcomposition. These ingredients include, but are not limited to,activators such as calcium or magnesium oxide; fatty acids such asstearic acid and salts thereof; fillers and reinforcers such as calciumor magnesium carbonate, silica, and aluminum silicates; plasticizerssuch as dialkyl esters of dicarboxylic acids; antidegradants; softeners;waxes; and pigments.

Polymerization Methods

Suitable processes useful in producing the block composites of theinvention may be found, for example, in US Patent ApplicationPublication No. 2008/0269412, published on Oct. 30, 2008, which isherein incorporated by reference. In particular, the polymerization isdesirably carried out as a continuous polymerization, preferably acontinuous, solution polymerization, in which catalyst components,monomers, and optionally solvent, adjuvants, scavengers, andpolymerization aids are continuously supplied to one or more reactors orzones and polymer product continuously removed therefrom. Within thescope of the terms “continuous” and “continuously” as used in thiscontext are those processes in which there are intermittent additions ofreactants and removal of products at small regular or irregularintervals, so that, over time, the overall process is substantiallycontinuous. Moreover, as previously explained, the chain shuttlingagent(s) may be added at any point during the polymerization includingin the first reactor or zone, at the exit or slightly before the exit ofthe first reactor, between the first reactor or zone and the second orany subsequent reactor or zone, or even solely to the second or anysubsequent reactor or zone. Due to the difference in monomers,temperatures, pressures or other difference in polymerization conditionsbetween at least two of the reactors or zones connected in series,polymer segments of differing composition such as comonomer content,crystallinity, density, tacticity, regio-regularity, or other chemicalor physical difference, within the same molecule are formed in thedifferent reactors or zones. The size of each segment or block isdetermined by continuous polymer reaction conditions, and preferably isa most probable distribution of polymer sizes.

Each reactor in the series can be operated under high pressure,solution, slurry, or gas phase polymerization conditions. In a multiplezone polymerization, all zones operate under the same type ofpolymerization, such as solution, slurry, or gas phase, but at differentprocess conditions. For a solution polymerization process, it isdesirable to employ homogeneous dispersions of the catalyst componentsin a liquid diluent in which the polymer is soluble under thepolymerization conditions employed. One such process utilizing anextremely fine silica or similar dispersing agent to produce such ahomogeneous catalyst dispersion wherein normally either the metalcomplex or the cocatalyst is only poorly soluble is disclosed in U.S.Pat. No. 5,783,512. A high pressure process is usually carried out attemperatures from 100° C. to 400° C. and at pressures above 500 bar (50MPa). A slurry process typically uses an inert hydrocarbon diluent andtemperatures of from 0° C. up to a temperature just below thetemperature at which the resulting polymer becomes substantially solublein the inert polymerization medium. Preferred temperatures in a slurrypolymerization are from 30° C., preferably from 60° C. up to 115° C.,preferably up to 100° C. Pressures typically range from atmospheric (100kPa) to 500 psi (3.4 MPa).

In all of the foregoing processes, continuous or substantiallycontinuous polymerization conditions are preferably employed. The use ofsuch polymerization conditions, especially continuous, solutionpolymerization processes, allows the use of elevated reactortemperatures which results in the economical production of the presentblock copolymers in high yields and efficiencies.

The catalyst may be prepared as a homogeneous composition by addition ofthe requisite metal complex or multiple complexes to a solvent in whichthe polymerization will be conducted or in a diluent compatible with theultimate reaction mixture. The desired cocatalyst or activator and,optionally, the shuttling agent may be combined with the catalystcomposition either prior to, simultaneously with, or after combinationof the catalyst with the monomers to be polymerized and any additionalreaction diluent.

At all times, the individual ingredients as well as any active catalystcomposition must be protected from oxygen, moisture and other catalystpoisons. Therefore, the catalyst components, shuttling agent andactivated catalysts must be prepared and stored in an oxygen andmoisture free atmosphere, preferably under a dry, inert gas such asnitrogen.

Without limiting in any way the scope of the invention, one means forcarrying out such a polymerization process is as follows. In one or morewell stirred tank or loop reactors operating under solutionpolymerization conditions, the monomers to be polymerized are introducedcontinuously together with any solvent or diluent at one part of thereactor. The reactor contains a relatively homogeneous liquid phasecomposed substantially of monomers together with any solvent or diluentand dissolved polymer. Preferred solvents include C₄₋₁₀ hydrocarbons ormixtures thereof, especially alkanes such as hexane or mixtures ofalkanes, as well as one or more of the monomers employed in thepolymerization. Examples of suitable loop reactors and a variety ofsuitable operating conditions for use therewith, including the use ofmultiple loop reactors, operating in series, are found in U.S. Pat. Nos.5,977,251, 6,319,989 and 6,683,149.

Catalyst along with cocatalyst and optionally chain shuttling agent arecontinuously or intermittently introduced in the reactor liquid phase orany recycled portion thereof at a minimum of one location. The reactortemperature and pressure may be controlled by adjusting thesolvent/monomer ratio, the catalyst addition rate, as well as by use ofcooling or heating coils, jackets or both. The polymerization rate iscontrolled by the rate of catalyst addition. The content of a givenmonomer in the polymer product is influenced by the ratio of monomers inthe reactor, which is controlled by manipulating the respective feedrates of these components to the reactor. The polymer product molecularweight is controlled, optionally, by controlling other polymerizationvariables such as the temperature, monomer concentration, or by thepreviously mentioned chain shuttling agent, or a chain terminating agentsuch as hydrogen, as is well known in the art. Connected to thedischarge of the reactor, optionally by means of a conduit or othertransfer means, is a second reactor, such that the reaction mixtureprepared in the first reactor is discharged to the second reactorwithout substantially termination of polymer growth. Between the firstand second reactors, a differential in at least one process condition isestablished. Preferably for use in formation of a copolymer of two ormore monomers, the difference is the presence or absence of one or morecomonomers or a difference in comonomer concentration. Additionalreactors, each arranged in a manner similar to the second reactor in theseries may be provided as well. Upon exiting the last reactor of theseries, the effluent is contacted with a catalyst kill agent such aswater, stream or an alcohol or with a coupling agent.

The resulting polymer product is recovered by flashing off volatilecomponents of the reaction mixture such as residual monomers or diluentat reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from 5 minutes to 8 hours, and preferablyfrom 10 minutes to 6 hours.

Alternatively, the foregoing polymerization may be carried out in a plugflow reactor with a monomer, catalyst, shuttling agent, temperature orother gradient established between differing zones or regions thereof,optionally accompanied by separated addition of catalysts and/or chainshuttling agent, and operating under adiabatic or non-adiabaticpolymerization conditions.

The catalyst composition may also be prepared and employed as aheterogeneous catalyst by adsorbing the requisite components on an inertinorganic or organic particulated solid, as previously disclosed. In apreferred embodiment, a heterogeneous catalyst is prepared byco-precipitating the metal complex and the reaction product of an inertinorganic compound and an active hydrogen containing activator,especially the reaction product of a tri (C₁₋₄ alkyl) aluminum compoundand an ammonium salt of a hydroxyaryltris(pentafluorophenyl)borate, suchas an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate. Whenprepared in heterogeneous or supported form, the catalyst compositionmay be employed in a slurry or a gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. As with a solution polymerization, the α-olefincomonomer or a mixture of different α-olefin monomers may be used inwhole or part as the diluent. Most preferably at least a major part ofthe diluent comprises the α-olefin monomer or monomers to bepolymerized.

TPV Compositions

The TPV compositions comprise at least a thermoplastic polymer as thematrix phase. Suitable thermoplastic polymer include, but are notlimited to, polyethylene, polypropylene, polycarbonate, olefin blockcopolymers, block composites, polystyrene, polyethylene terephthalate,nylon, branched polyethylene (such as high density polyethylene),branched polypropylene, branched polycarbonate, branched polystyrene,branched polyethylene terephthalate, and branched nylon. While otherthermoplastic polymers can be used, thermoplastic polyolefins, arepreferred. Further suitable thermoplastic polyolefins are thosedisclosed, for example, in U.S. Pat. No. 7,579,408, col. 25, line 4through Col. 28, line 28, which disclosure is herein incorporated byreference.

The TPV compositions also comprise at least a vulcanizable elastomer.Any vulcanizable elastomer may be used to form a TPV, provided that itcan be cross-linked (i.e., vulcanized) by a cross-linking agent.Vulcanizable elastomers, although thermoplastic in the uncured state,are normally classified as thermosets because they undergo anirreversible process of thermosetting to an unprocessable state.Preferred vulcanizable elastomers are those such as disclosed in U.S.Pat. No. 7,579,408, col. 29, line 61 through col. 31, line 40, whichdisclosure is herein incorporated by reference. Particularly preferredvulcanizable elastomers are EPDM, ethylene/α-olefins, olefin blockcopolymers and may also be block composites as defined herein.

Any cross-linking agent which is capable of curing an elastomer,preferably without substantially degrading and/or curing thethermoplastic polymer used in a TPV, can be used in embodiments of theinvention. A preferred cross-linking agent is phenolic resin. Othercuring agents include, but are not limited to, peroxides, azides,aldehyde-amine reaction products, vinyl silane grafted moieties,hydrosilylation, substituted ureas, substituted guanidines; substitutedxanthates; substituted dithiocarbamates; sulfur-containing compounds,such as thiazoles, imidazoles, sulfenamides, thiuramidisulfides,paraquinonedioxime, dibenzoparaquinonedioxime, sulfur; and combinationsthereof. Suitable cross-linking agents may also be used such as thosedisclosed in U.S. Pat. No. 7,579,408, col. 31, line 54 through col. 34,line 52, which disclosure is herein incorporated by reference.

The properties of a TPV may be modified, either before or aftervulcanization, by addition of ingredients which are conventional in thecompounding of EPDM rubber, thermoplastic polymer resin and blendsthereof. Examples of such ingredients include particulate filler such ascarbon black, amorphous precipitated or fumed silica, titanium dioxide,colored pigments, clay, talc, calcium carbonate, wollastonite, mica,montmorillonite, glass beads, hollow glass spheres, glass fibers, zincoxide and stearic acid, stabilizers, antidegradants, flame retardants,processing aids, adhesives, tackifiers, plasticizers, wax, discontinuousfibers, such as wood cellulose fibers and extender oils. Furtheradditives are those such as disclosed in U.S. Pat. No. 7,579,408, col.34, line 54 through col. 35, line 39, which disclosure is hereinincorporated by reference.

Thermoplastic vulcanizates are typically prepared by blending plasticand cured rubbers by dynamic vulcanization. The compositions can beprepared by any suitable method for mixing of rubbery polymers includingmixing on a rubber mill or in internal mixers such as a Banbury mixer.Further details on suitable methods are those such as disclosed in U.S.Pat. No. 7,579,408, col. 35, line 40 through col. 39, line 16, whichdisclosure is herein incorporated by reference.

Thermoplastic vulcanizate compositions are useful for making a varietyof articles such as tires, hoses, belts, gaskets, moldings and moldedparts. They are particularly useful for applications that require highmelt strength such as large part blow molding, foams, and wire cables.They also are useful for modifying thermoplastic resins, in particular,thermoplastic polymer resins. Additional TPV applications are disclosedin U.S. Pat. No. 7,579,408, col. 39, line 25 through col. 40, line 45,which disclosure is herein incorporated by reference.

Test Methods

The overall composition of each resin is determined by DSC, NMR, GPC,DMS, and TEM morphology. Xylene fractionation is further used toestimate the yield of block copolymer.

Differential Scanning Calorimetry (DSC)

Differential Scanning Calorimetry is performed on a TA Instruments Q1000DSC equipped with an RCS cooling accessory and an auto sampler. Anitrogen purge gas flow of 50 ml/min is used. The sample is pressed intoa thin film and melted in the press at about 190° C. and then air-cooledto room temperature (25° C.). About 3-10 mg of material is then cut,accurately weighed, and placed in a light aluminum pan (ca 50 mg) whichis later crimped shut. The thermal behavior of the sample isinvestigated with the following temperature profile: the sample israpidly heated to 190° C. and held isothermal for 3 minutes in order toremove any previous thermal history. The sample is then cooled to −90°C. at 10° C./min cooling rate and held at −90° C. for 3 minutes. Thesample is then heated to 150° C. at 10° C./min heating rate. The coolingand second heating curves are recorded.

¹³C Nuclear Magnetic Resonance (NMR)

Sample Preparation

The samples are prepared by adding approximately 2.7 g of a 50/50mixture of tetrachloroethane-d2/orthodichlorobenzene that is 0.025M inchromium acetylacetonate (relaxation agent) to 0.21 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C.

Data Acquisition Parameters

The data is collected using a Bruker 400 MHz spectrometer equipped witha Bruker Dual DUL high-temperature CryoProbe. The data is acquired using320 transients per data file, a 7.3 sec pulse repetition delay (6 secdelay+1.3 sec acq. time), 90 degree flip angles, and inverse gateddecoupling with a sample temperature of 125° C. All measurements aremade on non spinning samples in locked mode. Samples are homogenizedimmediately prior to insertion into the heated (130° C.) NMR Samplechanger, and are allowed to thermally equilibrate in the probe for 15minutes prior to data acquisition.

Gel Permeation Chromatography (GPC)

The gel permeation chromatographic system consists of either a Polymer

Laboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polypropylene)=0.645(M_(polystyrene)).

Polypropylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Fast-Temperature Rising Elution Fractionation (F-TREF)

In F-TREF analysis, the composition to be analyzed is dissolved inortho-dichlorobenzene and allowed to crystallize in a column containingan inert support (stainless steel shot) by slowly reducing thetemperature to 30° C. (at a preferred rate of 0.4° C./min). The columnis equipped with an infra-red detector. An F-TREF chromatogram curve isthen generated by eluting the crystallized polymer sample from thecolumn by slowly increasing the temperature of the eluting solvent(o-dichlorobenzene) from 30 to 140° C. (at a preferred rate of 1.5°C./min).

High Temperature Liquid Chromatography (HTLC)

HTLC is performed according to the methods disclosed in US PatentApplication Publication No. 2010-0093964 and U.S. patent applicationSer. No. 12/643,111, filed Dec. 21, 2009, both of which are hereinincorporated by reference. Samples are analyzed by the methodologydescribed below.

A Waters GPCV2000 high temperature SEC chromatograph was reconfigured tobuild the HT-2DLC instrumentation. Two Shimadzu LC-20AD pumps wereconnected to the injector valve in GPCV2000 through a binary mixer. Thefirst dimension (D1) HPLC column was connected between the injector anda 10-port switch valve (Valco Inc). The second dimension (D2) SEC columnwas connected between the 10-port valve and LS (Varian Inc.), IR(concentration and composition), RI (refractive index), and IV(intrinsic viscosity) detectors. RI and IV were built-in detector inGPCV2000. The IRS detector was provided by PolymerChar, Valencia, Spain.

Columns: The D1 column was a high temperature Hypercarb graphite column(2.1×100 mm) purchased from Thermo Scientific. The D2 column was aPLRapid-H column purchased from Varian (10×100 mm).

Reagents: HPLC grade trichlorobenzene (TCB) was purchased from FisherScientific. 1-Decanol and decane were from Aldrich.2,6-Di-tert-butyl-4-methylphenol (Ionol) was also purchased fromAldrich.

Sample Preparation: 0.01-0.15 g of polyolefin sample was placed in a10-mL Waters autosampler vial. 7-mL of either 1-decanol or decane with200 ppm lonol was added to the vial afterwards. After sparging helium tothe sample vial for about 1 min, the sample vial was put on a heatedshaker with temperature set at 160° C. The dissolution was done byshaking the vial at the temperature for 2 hr. The vial was thentransferred to the autosampler for injection. Please note that theactual volume of the solution was more than 7 mL due to the thermalexpansion of the solvent.HT-2DLC: The D1 flow rate was at 0.01 mL/min. The composition of themobile phase was 100% of the weak eluent (1-decanol or decane) for thefirst 10 min of the run. The composition was then increased to 60% ofstrong eluent (TCB) in 489 min. The data were collected for 489 min asthe duration of the raw chromatogram. The 10-port valve switched everythree minutes yielding 489/3=163 SEC chromatograms. A post-run gradientwas used after the 489 min data acquisition time to clean andequilibrate the column for the next run:Clean Step:

-   -   1. 490 min: flow=0.01 min; // Maintain the constant flow rate of        0.01 mL/min from 0-490 min.    -   2. 491 min: flow=0.20 min; // Increase the flow rate to 0.20        mL/min.    -   3. 492 min: % B=100; // Increase the mobile phase composition to        100% TCB    -   4. 502 min: % B=100; // Wash the column using 2 mL of TCB        Equilibrium Step:    -   5. 503 min: % B=0; // Change the mobile phase composition to        100% of 1-decanol or decane    -   6. 513 min: % B=0; // Equilibrate the column using 2 mL of weak        eluent    -   7. 514 min: flow=0.2 mL/min; // Maintain the constant flow of        0.2 mL/min from 491-514 min    -   8. 515 min: flow=0.01 mL/min; // Lower the flow rate to 0.01        mL/min.

After step 8, the flow rate and mobile phase composition were the sameas the initial conditions of the run gradient. The D2 flow rate was at2.51 mL/min. Two 60 μL loops were installed on the 10-port switch valve.30-μL of the eluent from D1 column was loaded onto the SEC column withevery switch of the valve. The IR, LS15 (light scattering signal at15°), LS90 (light scattering signal at 90°), and IV (intrinsicviscosity) signals were collected by EZChrom through a SS420Xanalogue-to-digital conversion box. The chromatograms were exported inASCII format and imported into a home-written MATLAB software for datareduction. Using an appropriate calibration curve of polymer compositionand retention volume, of polymers that are of similar nature of the hardblock and soft block contained in the block composite being analyzed.Calibration polymers should be narrow in composition (both molecularweight and chemical composition) and span a reasonable molecular weightrange to cover the composition of interest during the analysis. Analysisof the raw data was calculated as follows, the first dimension HPLCchromatogram was reconstructed by plotting the IR signal of every cut(from total IR SEC chromatogram of the cut) as a function of the elutionvolume. The IR vs. D1 elution volume was normalized by total IR signalto obtain weight fraction vs. D1 elution volume plot. The IRmethyl/measure ratio was obtained from the reconstructed IR measure andIR methyl chromatograms. The ratio was converted to composition using acalibration curve of PP wt. % (by NMR) vs. methyl/measure obtained fromSEC experiments. The MW was obtained from the reconstructed IR measureand LS chromatograms. The ratio was converted to MW after calibration ofboth IR and LS detectors using a PE standard. The weight % of isolatedPP is measured as the area that corresponds to the hard blockcomposition based on the isolated peak and the retention volume asdetermined by a composition calibration curve.

Dynamic Mechanical Spectroscopy (DMS)

The dynamic mechanical measurements (loss and storage modulus vs.temperature) are measured on TA instruments ARES. The dynamic modulusmeasurements are performed in torsion on a solid bar of ca. 2 mmthickness, 5 mm wide and ca. 10 mm in length. The data is recorded at aconstant frequency of 10 rad/s and at a heating/cooling rate of 5°C./min. The temperature sweeps are performed from −50 to 190 C at 5°C./min.

Transmission Electron Microscopy

Polymer films are prepared by compression molding followed by fastquenching. The polymer is pre-melted at 190° C. for 1 minute at 1000 psiand then pressed for 2 minutes at 5000 psi and then quenched betweenchilled platens (15-20° C.) for 2 minutes.

The compression molded films are trimmed so that sections could becollected near the core of the films. The trimmed samples arecryopolished prior to staining by removing sections from the blocks at−60° C. to prevent smearing of the elastomer phases. The cryo-polishedblocks are stained with the vapor phase of a 2% aqueous rutheniumtetraoxide solution for 3 hrs at ambient temperature. The stainingsolution is prepared by weighing 0.2 gm of ruthenium (III) chloridehydrate (RuCl₃×H₂O) into a glass bottle with a screw lid and adding 10ml of 5.25% aqueous sodium hypochlorite to the jar. The samples areplaced in the glass jar using a glass slide having double sided tape.The slide is placed in the bottle in order to suspend the blocks about 1inch above the staining solution. Sections of approximately 90nanometers in thickness are collected at ambient temperature using adiamond knife on a Leica EM UC6 microtome and placed on 600 mesh virginTEM grids for observation.

Image Collection—TEM images are collected on a JEOL JEM-1230 operated at100 kV accelerating voltage and collected on a Gatan-791 and 794 digitalcameras.

Xylene Soluble Fractionation Analysis

A weighed amount of resin is dissolved in 200 ml o-xylene under refluxconditions for 2 hours. The solution is then cooled in a temperaturecontrolled water bath to 25° C. to allow the crystallization of thexylene insoluble (XI) fraction. Once the solution is cooled and theinsoluble fraction precipitates from the solution, the separation of thexylene soluble (XS) fraction from the xylene insoluble fraction is doneby filtration through a filter paper. The remaining o-xylene solution isevaporated from the filtrate. Both XS and XI fractions are dried in avacuum oven at 100° C. for 60 min and then weighed. Alternatively, ifthe solution crystallization temperature of the soft block polymer isabove room temperature, the fractionation step can be carried out at atemperature 10-20° C. above the soft blocks crystallization temperaturebut below the hard blocks crystallization temperature. The temperatureof separation can be determined by TREF or CRYSTAF measurement asdescribed by reference, TREF and CRYSTAF technologies for PolymerCharacterization, Encyclopedia of Analytical Chemistry. 2000 Issue,Pages 8074-8094. This fractionation can be carried out in a laboratoryheated dissolution and filtration apparatus or a fractionationinstrument such as the Preparatory mc^(g) (available from Polymer Char,Valencia, Spain).

Melt Index and Melt Flow Rate:

Melt Index, or I₂ is measured in grams per 10 minutes, is done inaccordance with ASTM D 1238, condition 190° C./2.16 kg. The MFR of thePP resins is measured in accordance to ASTM D 1238, condition 230°C./2.16 kg.

Shore A Hardness

Shore A hardness is carried out according to ASTM D 2240.

Compression Set:

Compression set is measured according to ASTM D 395 at 70° C.

Tensile Properties:

Tensile strength and ultimate elongation are carried out according toASTM D-412.

Atomic Force Microscopy (AFM)

Samples are polished under cryogenic conditions using a Leica UCT/FCSmicrotome operated at −120° C. Some thin sections (about 160 nm) are cutfrom the sample and placed on the mica surface for AFM analysis.Topography and phase images are captured at ambient temperature by usinga Digital Instruments (now Veeco) Multi-Mode AFM equipped with aNanoScope IV controller. Nano-sensor probes with a spring constant of 55N/m and a resonant frequency in the vicinity of 167 kHz are used forphase imaging. The samples are imaged at a frequency of 0.5-2 Hz and aset point ratio of ˜0.8.

Test Methods for TPV Compositions

Gel Content

Gel content is measured by small scale Soxhlet extraction method.Samples are cut into small pieces ranging from about 35 mg to 86 mg.Three pieces of each sample are individually weighed to 4-place accuracyon a top-loading electronic analytical balance. Each piece is placedinside a small cylinder composed of aluminum window screen. The ends ofthe cylinders are closed with ordinary paper staples. Six aluminumcylinders are placed inside one fritted glass extraction thimble. Thethimbles are placed in jacketed Soxhlet extractors and extractedovernight with refluxing xylenes. At the end of the minimum 12 hourextraction, the still warm thimbles are quenched in methanol. Themethanol precipitates the gel and makes it easier to remove the gelsintact from the cylinders. The cylinders containing precipitated gelsare purged briefly with nitrogen to drive off free methanol. The gelsare removed from the aluminum cylinders with forceps and placed onaluminum weighing pans. The pans with gels are vacuum dried for 1 hourat 125° C. The dried, cool gels are removed from aluminum weighing pansand weighed directly on the top-loading analytical balance. The dryextracted gel weight is divided by the starting weight to give thepercent gel content.

Atomic Force Microscopy (AFM)

Samples are polished under cryogenic conditions using a Leica UCT/FCSmicrotome operated at −120° C. Thin sections (about 160 nm) are cut fromsample and placed on a mica surface for AFM analysis. Topography andphase images are captured at ambient temperature by using a DigitalInstruments (now Veeco) Multi-Mode AFM equipped with a NanoScope IVcontroller. Nano-sensor probes with a spring constant 55 N/m and aresonant frequency in the vicinity of 167 kHz are used for phaseimaging. The samples are imaged at a frequency of 0.5-2 Hz and a setpoint ratio of ˜0.8

Differential Scanning Calorimetry (DSC)

Differential scanning Calorimetry (DSC) is performed on a TA InstrumentsQ100 DSC V9.8 Build 296 using Universal V3.7A analysis software from TAInstruments. Samples are rapidly heated to 230° C. and held isothermallyfor 3 minutes in order to remove any previous heat history. The sampleare then cooled to −90° C. at 10° C./minute cooling rate and held at−90° C. for 3 minutes. The samples are then heated to 230° C. at 10°C./minute heating rate. The first cooling and second heating curves arerecorded.

Dynamic Mechanical Spectroscopy (DMS)

Constant temperature dynamic frequency sweeps in the frequency range of0.1 to 100 rad/s are performed under nitrogen purge using a TAInstruments Advanced Rheometric Expansion System (ARES) equipped with 25mm parallel plates. TPO or TPV samples are die cut from compression orinjection-molded plaques into 3 mm thick×1 inch diameter circularspecimens. The sample is placed on the plate and allowed to melt for 5minutes. The plates are then closed to 2.1 mm, the sample trimmed, andthe gap closed to 2.0 mm before starting the test. The method has anadditional 5 minute delay built-in to allow for temperatureequilibration. Both TPO and TPV samples are measured at 230° C. Thestrain amplitude is held constant at 10%. The stress response isreported as the storage moduli (G′), loss moduli (G″) and the complexviscosity (η*)

Dynamic Mechanical Thermal Analysis (DMTA)

The solid state dynamic mechanical properties of the materials aremeasured on a Rheometric Dynamic Analyzer (RDA III) intorsional-rectangular mode on a rectangular bar. Specimens with 3 mmthickness and 12.5 mm width are die cut from compression orinjection-molded plaques. The initial gap is set to 10 mm for allsamples. The temperature is varied from −100° C. to 200° C. at a rate of5° C./min, and the storage moduli (G′), loss moduli (G″) are monitoredat a constant rate of 10 rad/s. As the sample expanded during heating,the gap is adapted to minimize the normal load on the sample. The strainamplitude is allowed to vary from 0.05% at low temperature to 4% at hightemperature.

Shore A Hardness

Hardness measurements are taken with a Shore A type durometer. Thedurometer is placed onto a plaque of ˜3 mm thickness, prepared bycompression or injection molding.

Compression Set

Compression set is measured according to ASTM D 395 at 70° C. and 120°C. Pucks of 29.mm (±0.5 mm) are extracted from the compression orinjection molded plaques of ˜3 mm thickness. For each sample, four pucksare inspected for notches, uneven thickness and inhomogeneity, and arestacked such that the total height is 12.5 mm (±0.5 mm), equating tocompressive strain of 25%. Compression set is performed on two specimensfor each sample at the two temperatures.

The stacked pucks are placed in the compressive device and locked intoplace; the apparatus is then placed at the appropriate temperature forspecified time (22 hrs for 70° C. and 72 hrs for 120° C.). In this testthe stress is released at the test temperature and the thickness of thesample is measured after a 30 min. equilibration period at roomtemperature.

Compression set is a measure of the degree of recovery of a samplefollowing compression and is calculated according to the equationCS=(H₀−H₂)/(H₀−H₁); where H₀ is the original thickness of the sample, H₁is the thickness of the spacer bar used and H₂ is the final thickness ofthe sample after removal of the compressive force.

Stress-Strain Properties

Tensile properties are measured at room temperature following ASTMD-412, on micro-tensile specimens that are die cut from the samecompression or injection molded plaques in the mill direction. Thetensile strain is calculated from the ratio of the increment of thelength between clamps to the initial gauge length. The tensile stress isdetermined from dividing the tensile load by the initial cross sectionof the sample.

Table A lists a summary of all characterization methods used in thisstudy and specific conditions.

TABLE A Summary of characterization methods and conditions Test andDescription ASTM # Test Condition Gel Content / 12 hours in boilingxylene Shore A Hardness D2240 10 s delay Tensile Properties* D1708Microtensiles--Die 84 Compression Set D395B 25% strain, 22 hrs @ 70° C.25% strain, 70 hrs @ 120° C. DSC / −90° C. to 230° C. DMS D3838 230° C.DMTA E313-73, D1925-70 0.05% to 0.4% strain AFM / Tapping mode TEM /Back scattering *All tensile bars are cut (and thus pulled) in the milldirection

EXAMPLES Examples

General

Catalyst-1([[rel-2′,2′″-[(1R,2R)-1,2-cylcohexanediylbis(methyleneoxy-κO)]bis[3-(9H-carbazol-9-yl)-5-methyl[1,1′-biphenyl]-2-olato-κO]](2-)]dimethyl-hafnium)and cocatalyst-1 a mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate, prepared by reaction of a long chaintrialkylamine (Armeen™ M2HT, available from Akzo-Nobel, Inc.), HCl andLi[B(C₆F₅)₄], substantially as disclosed in U.S. Pat. No. 5,919,9883,Ex. 2., are purchased from Boulder Scientific and used without furtherpurification. CSA-1 (diethylzinc or DEZ) and modified methylalumoxane(MMAO) were purchased from Akzo Nobel and used without furtherpurification. The solvent for the polymerization reactions is ahydrocarbon mixture (SBP 100/140) obtainable from Shell Chemical Companyand purified through beds of 13-X molecular sieves prior to use.

All examples except A1, E1, U1 and Y1 have an iPP hard block. Runs Bthrough D have a semi-crystalline, ethylene-propylene soft blockcontaining 60-65 wt % C2 while runs F through H have an amorphous,ethylene-propylene soft block containing 40 wt % C2. With increasingalphabetical letter, the weight fraction and length of the iPP hardblock is independently controlled from 30 to 60 weight percent byincreasing the production rate in the reactor (in this case, reactor 2).

Examples V1, W1, X1 and Y1, Z1, AA are similar in design to B, C, D butmade at different reactor conditions. The effect of higher propyleneconversion and reactor temperature will be discussed later.

All examples are run with no hydrogen. The CSA concentration in Reactor1 for all examples is 153 mmol/kg. The MMAO concentration in Reactor 2for all examples is 6 mmol/kg.

Samples A1-D1

Inventive propylene/ethylene copolymers were prepared using twocontinuous stirred tank reactors (CSTR) connected in series. Eachreactor is hydraulically full and set to operate at steady stateconditions. Sample A1 is prepared by flowing monomers, solvent,catalyst-1, cocatalyst-1, and CSA-1 to the first reactor according tothe process conditions outlined in Table 1. To prepare sample B1, thefirst reactor contents as described in Table 1A were flowed to a secondreactor in series. Additional catalyst-1 and cocatalyst-1 were added tothe second reactor, as well as a small amount of MMAO as a scavenger.Samples C1 and D1 were prepared by controlling the conditions of the tworeactors as described in Table 1A and 1B.

Samples E1-AB1

Each set of diblock samples F1-H1, V1-X1, Y1-AB1 were prepared as abovefor examples B1-D1 but according to the process conditions outlined inTable 1A and 1B. For each set, a first reactor product (E1, U1, Y1) isprepared targeting the first block composition.

TABLE 1A First reactor process conditions to produce diblock copolymersB1-D1, F1-H1, V1-X1, Z1-AB1. Catalyst Cocatalyst Solvent PropyleneEthylene Catalyst sol. Cocatalyst sol. CSA C3 Calculated feed feed feedTemp conc flow conc. Flow flow conversion split Efficiency Example(kg/hr) (kg/hr) (Kg/Hr) ° C. (mmol/Kg) (g/hr) (mmol/kg) (g/hr) (g/hr)(%) (%) (gPoly/gM)*10⁻⁶ A1§ 25 0.87 1.4 90 0.3 47 0.36 47 230 91 1000.79 B1 25 0.87 1.4 90 0.3 43 0.36 43 222 91 66.6 0.87 C1 25 0.87 1.4 900.3 40 0.36 40 222 90 50 0.93 D1 17.5 0.65 1.05 90 0.3 22 0.36 22 165 9040 1.27 E1§ 14 1.06 0.65 90 0.3 14 0.36 24 120 90 100 2.00 F1 14 1.060.65 91 0.3 16 0.36 25 120 90 66.6 1.75 G1 14 1.06 0.65 92 0.3 16.5 0.3620.1 120 91 50 1.70 H1 14 1.06 0.65 91 0.3 20 0.36 20 120 90 40 1.40 U1§17.5 0.61 1.02 91 0.3 50 0.36 50 162 95 100 0.56 V1 17.5 0.61 1.02 900.3 50 0.36 50 160 96 66.6 0.56 W1 17.5 0.61 1.02 91 0.3 52 0.36 52 16096 50 0.54 X1 16.3 0.61 1.02 91 0.3 52 0.36 52 160 95 40 0.54 Y1§ 110.66 1.08 120 0.03 140 0.036 140 163 91 100 2.00 Z1 11 0.66 1.02 1200.03 140 0.036 140 163 91 66.6 2.00 AA1 11 0.66 1.08 120 0.03 140 0.036140 163 91 50 2.00 AB1 11 0.66 1.08 120 0.03 140 0.03 140 163 91 40 2.00§1^(st) reactor products only

TABLE 1B Second reactor process conditions to produce diblock copolymersB1-D1, F1-H1, V1-X1, Z1-AB1. Solvent Propylene Catalyst CatalystCocatalyst Cocatalyst MMAO C3 feed feed Temp conc sol. Flow conc. sol.Flow flow conversion Efficiency Example (kg/hr) (kg/hr) ° C. (mmol/Kg)(g/hr) (mmol/kg) (g/hr) (gr/hr) (%) (gPoly/gM) *10⁻⁶ A1§ B1 13 1.11 900.3 90 0.36 90 45 91 0.41 C1 20 2.22 90 0.3 120 0.36 120 50 91 0.46 D121 2.5 90 0.3 177 0.36 177 50 91 0.32 E1§ F1 10 0.83 91 0.3 24 0.36 24100 91 1.11 G1 16 1.66 90.2 0.3 92 0.36 92 80 91 0.52 H1 21 2.5 90 0.3175 0.36 175 80 91 0.37 U1§ V1 10 0.78 90.2 0.3 90 0.36 90 100 96 0.30W1 15 1.36 90.2 0.3 177 0.36 177 110 95 0.24 X1 20.5 2.36 90.5 0.3 2600.36 260 220 95 0.22 Y1§ Z1 10 0.83 120 0.03 160 0.036 160 100 90 1.40AA1 11 1.66 120.1 0.03 250 0.036 250 100 90 1.44 AB1 16 2.5 120 0.3 600.3 60 100 90 0.95 §1^(st) reactor products only

Preparation of Fractionated Samples

Two to four grams of polymer is dissolved in 200 ml o-xylene underreflux conditions for 2 hours. The solution is then cooled in atemperature controlled water bath to 25° C. to allow the crystallizationof the xylene insoluble fraction. Once the solution is cooled and theinsoluble fraction precipitates from the solution, the separation of thexylene soluble fraction from the xylene insoluble fraction is done byfiltration through a filter paper. The remaining o-xylene solvent isevaporated from the filtrate. Both xylene soluble (XS) and xyleneinsoluble (XI) fractions are dried in a vacuum oven at 100° C. for 60min and then weighed.

For each set of samples, the xylene insoluble fraction is given thenumber “2” and the xylene soluble fraction the number “3”. For example,sample B1 is subjected to the extraction procedure to produce sample B2(the xylene insoluble fraction) and sample B3 (the xylene solublefraction.

Table 2 shows the analytical results for runs B1 through AB1. Themolecular weight distributions of the polymers are relatively narrowwith Mw/Mn's ranging from 2.1-2.3 for samples B1 through D1, and 2.2-2.8for samples F1 through H1. For samples V1 through AB1, Mw/Mn's rangefrom 2.1-2.5. For the corresponding xylene insoluble and solublefractions for each of the runs (designated by the number 2 or 3), theMw/Mn's range from 2.0 to 2.8.

Table 2 also shows the wt % of isolated PP identified by HighTemperature Liquid Chromatography separation. The amount of isolated PPindicates to the amount of PP that is not incorporated into the blockcopolymer. The weight fraction of isolated PP and the weight fraction ofxylene solubles subtracted from 1 can be related to the yield of diblockpolymer produced.

The molecular weight distributions of the polymers are relatively narrowwith Mw/Mn's ranging from 2.1-2.3 for samples B1 through D1, and 2.2-2.8for samples F1 through H1. For samples V1 through AB1, Mw/Mn's rangefrom 2.1-2.5. For the corresponding xylene insoluble and solublefractions for each of the runs (designated by the number 2 or 3), theMw/Mn's range from 2.0 to 2.8.

TABLE 2 Analytical Summary Examples B1-AB1 and Fractions Melt Wt % PP Wt% from Mw Wt % Tm Tc Enthalpy Tg from HTLC Example Extraction Kg/molMw/Mn C₂ (° C.) (° C.) (J/g) (° C.) Separation B1 NA 123 2.2 45 130 8543 −46 11.8 B2 37.8 165 2.0 20.3 131 93 80 ND 26 B3 62.2 124 2.1 64.4 23   26.11 27 −49 <0.1 C1 NA 128 2.1 34 134 92 56 −57 — C2 50.4 243 2.812.4 137 99 83 ND — C3 49.6 136 2.1 61.1  9  5 26 −51 — D1 NA 180 2.3 26138 93 56 −49 28.1 D2 63.3 284 2.1 10.1 138 100  86 ND 44.1 D3 37.7 1302.1 61.5  11  6 28 −51 <0.1 F1 NA 149 2.2 27 135 91 28 −50 22 F2 33.9207 2.3 8.3 137 99 80 ND 49 F3 66.1 143 2.1 38.5 ND ND 1.4 −51 0.8 G1 NA210 2.5 18.2 139 99 49 −52 — G2 51.9 302 2.3 5.8 140 102  76 −51 — G348.1 139 2.1 39.8 ND ND ND ND — H1 NA 251 2.8 14.8 141 103  61   −53.5 —H2 60.6 371 2.5 4.4 142 105  83.5 ND — H3 39.4 141 2.2 38.1 ND ND 1.4−51 — V1 NA 120 2.1 45   131.1   88.3 59.3 −44 — V2 41.7 — — 20.4 — — —— — V3 58.3 — — 67 — — — — — W1 NA 148 2.1 34   135.2   96.7 68.2  −44.2 — W2 57   — — 15.9 — — — — — W3 43.0 — — 67.8 — — — — — X1 NA198 2.5 26   138.4  101.4 73.7   −48.2 — X2 65.5 — — 11.3 — — — — — X334.5 — — 64.1 — — — — — Z1 NA 114 2.2 27   120.4   71.4 54.4   −43.9 —Z2 31.7 — — 18.9 — — — — — Z3 68.3 — — 65.9 — — — — — AA1 NA 136 2.2 20  129.6   88.8 64.1   −45.3 — AA2 50.7 — — 14.9 — — — — — AA3 49.3 — —69 — — — — — AB1 NA 168 2.4 15   134.7   97.6 67.9   −47.5 — AB2 64.4 —— 11.8 — — — — — AB3 35.6 — — 67.7 — — — — —

FIG. 1 shows the DSC melting curve for the B1 sample. The peak at 130°C. corresponds to the iPP “hard” polymer and the broader peak at 30° C.corresponds to the EP “soft” polymer; the glass transition temperatureat −46° C. also corresponds to the EP “soft” polymer containing 64 wt %ethylene (C₂).

FIG. 2 shows the DSC melting curve for the F1 sample. The peak at 135°C. corresponds to the iPP “hard” polymer and the absence ofcrystallinity below room temperature corresponds to the EP “soft”polymer containing 40 wt % C₂. The −50° C. Tg confirms the presence ofthe EP “soft” polymer containing 40 wt % C₂.

The presence of block copolymer can alter the crystallizationcharacteristics of a polymer chain if measured by TREF or solutionfractionation. FIG. 3 compares the TREF profiles of samples B1 throughD1. The TREF profiles are consistent with the DSC results, showing ahighly crystalline fraction (elution above 40° C.) and a lowcrystallinity, soluble fraction (remaining material that elutes at lessthan 40° C.). The elution temperature increases with the amount of iPPpresent. An EP block connected to an iPP block may enhance the chains'solubility in the solvent and/or interfere with the crystallization ofthe iPP block.

FIGS. 4 and 5 show the corresponding DSC curves of the fractions of B2,B3 and F2, F3.

In this analysis, the xylene soluble fraction is an estimate of theamount of non-crystallizable soft polymer. For the xylene solublefractions from samples B1-D1, the weight percent of ethylene is between61 and 65 wt % ethylene with no detection of residual isotacticpropylene. The DSC of the xylene soluble fraction confirms that no highcrystallinity polypropylene is present.

Conversely, the insoluble fraction (designated as number 2) can containan amount of iPP polymer and iPP-EP diblock. Since the crystallizationand elution of the polymer chain is governed by its longestcrystallizable propylene sequence, the diblock copolymer willprecipitate along with the iPP polymer. This is verified by the NMR andDSC analysis that shows an appreciable, and otherwise unexplainable,amount of ethylene present in the “insoluble” fraction. In a typicalseparation of an iPP and EP rubber blend, the isotactic PP will becleanly separated by this analysis. The fact that there is “additional”ethylene present in the insoluble fraction, verifies that a fraction ofdiblock is present. By accounting for the total mass balance of monomerbetween the fractions, a block composite index can be estimated.

Another indication of the presence of diblock is the increase inmolecular weight of the insoluble fractions with the increasing amountof iPP. As the polymer chains are being coordinatively coupled whilepassing from the first reactor to the second reactor, it is expectedthat the molecular weight of the polymer will increase. Table 3 showsthat the molecular weight of the soluble fractions remains relativelyconstant (120-140 kg/mol). This is expected because the reactorconditions to make the EP soft block were unchanged from run to run.However, the molecular weight of the insoluble fractions increases withthe increase in production rate of reactor 2, to create longer iPPblocks.

Estimating the Block Composite Index

The inventive examples show that the insoluble fractions contain anappreciable amount of ethylene that would not otherwise be present ifthe polymer was simply a blend of iPP homopolymer and EP copolymer. Toaccount for this “extra ethylene”, a mass balance calculation can beperformed to estimate a block composite index from the amount of xyleneinsoluble and soluble fractions and the weight % ethylene present ineach of the fractions.

A summation of the weight % ethylene from each fraction according toequation 1 results in an overall weight % ethylene (in the polymer).This mass balance equation can also be used to quantify the amount ofeach component in a binary blend or extended to a ternary, orn-component blend.Wt % C ₂ _(Overall) =w _(Insoluble)(wt % C ₂ _(Insoluble) )+w_(soluble)(wt % C ₂ _(soluble) )  Eq. 1

Applying equations 2 through 4, the amount of the soft block (providingthe source of the extra ethylene) present in the insoluble fraction iscalculated. By substituting the weight % C₂ of the insoluble fraction inthe left hand side of equation 2, the weight % iPP hard and weight % EPsoft can be calculated using equations 3 and 4. Note that the weight %of ethylene in the EP soft is set to be equal to the weight % ethylenein the xylene soluble fraction. The weight % ethylene in the iPP blockis set to zero or if otherwise known from its DSC melting point or othercomposition measurement, the value can be put into its place.

$\begin{matrix}{{{Wt}\mspace{14mu}\%\mspace{14mu} C_{2_{{Overall}\mspace{14mu}{or}\mspace{14mu}{xylene}\mspace{14mu}{insoluble}}}} = {{w_{iPPHard}\left( {{wt}\mspace{14mu}\%\mspace{14mu} C_{2_{iPP}}} \right)} + {w_{EPsoft}\left( {{wt}\mspace{14mu}\%\mspace{14mu} C_{2_{EPsoft}}} \right)}}} & {{Eq}.\mspace{14mu} 2} \\{\mspace{79mu}{w_{iPPhard} = \frac{{{wt}\mspace{14mu}\%\mspace{14mu} C_{2_{{overall}\mspace{14mu}{or}\mspace{14mu}{xyleneinsoluble}}}} - {{wt}\mspace{14mu}\%\mspace{14mu} C_{2_{EPsoft}}}}{{{wt}\mspace{14mu}\%\mspace{14mu} C_{2_{iPPhard}}} - {{wt}\mspace{14mu}\%\mspace{14mu} C_{2_{EPsoft}}}}}} & {{Eq}.\mspace{14mu} 3} \\{\mspace{79mu}{w_{EPsoft} = {1 - w_{iPPHard}}}} & {{Eq}.\mspace{14mu} 4}\end{matrix}$

After accounting for the ‘additional’ ethylene present in the insolublefraction, the only way to have an EP copolymer present in the insolublefraction, the EP polymer chain must be connected to an iPP polymer block(or else it would have been extracted into the xylene soluble fraction).Thus, when the iPP block crystallizes, it prevents the EP block fromsolubilizing.

To estimate the block composite index, the relative amount of each blockmust be taken into account. To approximate this, the ratio between theEP soft and iPP hard is used. The ratio of the EP soft polymer and iPPhard polymer can be calculated using Equation 2 from the mass balance ofthe total ethylene measured in the polymer. Alternatively it could alsobe estimated from a mass balance of the monomer and comonomerconsumption during the polymerization. Refer to Table 3 for theestimated ratio of iPP and EP present in the diblock copolymer for allthe runs. The weight fraction of iPP hard and weight fraction of EP softis calculated using Equation 2 and assumes the iPP hard contains noethylene. The weight % ethylene of the EP soft is the amount of ethylenepresent in the xylene soluble fraction.

TABLE 3 Block Composite Index Estimations for Examples B1 through AB3Block wt fraction wt fraction Composite Sample EP Soft iPP Hard Index B10.30 0.70 0.16 B2 0.32 0.68 0.42 B3 0 100 0 C1 0.56 0.44 0.17 C2 0.200.80 0.34 C3 0 100 0 D1 0.42 0.58 0.22 D2 0.16 0.84 0.35 D3 0 100 0 F10.70 0.30 0.10 F2 0.22 0.78 0.29 F3 0 100 0 G1 0.46 0.54 0.15 G2 0.150.85 0.29 G3 0 100 0 H1 0.39 0.61 0.18 H2 0.12 0.88 0.29 H3 0 100 0 V10.67 0.33 0.18 V2 0.30 0.70 0.43 V3 0 100 0 W1 0.50 0.50 0.24 W2 0.230.77 0.42 W3 0 100 0 X1 0.41 0.59 0.25 X2 0.18 0.82 0.39 X3 0 100 0 Z10.41 0.59 0.12 Z2 0.29 0.71 0.38 Z3 0 100 0 AA1 0.29 0.71 0.18 AA2 0.220.78 0.35 AA3 0 100 0 AB1 0.22 0.78 0.24 AB2 0.17 0.83 0.38 AB3 0 100 0

For example, if an inventive iPP-EP polymer contains an overall of 47 wt% C₂ and is made under the conditions to produce an EP soft polymer with67 wt % C₂ and an iPP homopolymer containing zero ethylene, the amountof EP soft and iPP hard is 70 wt % and 30 wt %, respectively (ascalculated using Equations 3 and 4). If the percent of EP is 70 wt % andthe iPP is 30 wt %, the relative ratio of the EP:iPP blocks could beexpressed as 2.33:1.

Hence, if one skilled in the art, carries out a xylene extraction of thepolymer and recovers 40 wt % insoluble and 60 wt % soluble, this wouldbe an unexpected result and this would lead to the conclusion that afraction of inventive block copolymer was present. If the ethylenecontent of the insoluble fraction is subsequently measured to be 25 wt %C₂, Equations 2 thru 4 can be solved to account for this additionalethylene and result in 37.3 wt % EP soft polymer and 62.7 wt % iPP hardpolymer present in the insoluble fraction.

Since the insoluble fraction contains 37.3 wt % EP copolymer, it shouldbe attached to an additional 16 wt % of iPP polymer based on the EP:iPPblock ratio of 2.33:1. This brings the estimated amount of diblock inthe insoluble fraction to be 53.3 wt %. For the entire polymer(unfractionated), the composition is described as 21.3 wt % iPP-EPDiblock, 18.7 wt % iPP polymer, and 60 wt % EP polymer. As thecompositions of these polymers are novel, the term block composite index(BCI) is herein defined to equal the weight percentage of diblockdivided by 100% (i.e. weight fraction). The value of the block compositeindex can range from 0 to 1, wherein 1 would be equal to 100% inventivediblock and zero would be for a material such as a traditional blend orrandom copolymer. For the example described above, the block compositeindex for the block composite is 0.213. For the insoluble fraction, theBCI is 0.533, and for the soluble fraction the BCI is assigned a valueof zero.

Depending on the estimations made of the total polymer composition andthe error in the analytical measurements which are used to estimate thecomposition of the hard and soft blocks, between 5 to 10% relative erroris possible in the computed value of the block composite index. Suchestimations include the wt % C2 in the iPP hard block as measured fromthe DSC melting point, NMR analysis, or process conditions; the averagewt % C2 in the soft block as estimated from the composition of thexylene solubles, or by NMR, or by DSC melting point of the soft block(if detected). But overall, the block composite index calculationreasonably accounts for the unexpected amount of ‘additional’ ethylenepresent in the insoluble fraction, the only way to have an EP copolymerpresent in the insoluble fraction, the EP polymer chain must beconnected to an iPP polymer block (or else it would have been extractedinto the xylene soluble fraction).

More specifically, example H1, contains an overall of 14.8 wt % C₂ andthe weight % C2 in the xylene solubles (H3) was measured to be 38.1 wt %(as a representation of the composition of the EP soft polymer) and aniPP homopolymer containing zero ethylene, the amount of EP soft and iPPhard is 61 wt % and 39 wt %, respectively (as calculated using Equations3 and 4). If the percent of EP is 61 wt % and the iPP is 39 wt %, therelative ratio of the EP:iPP blocks could be expressed as 1.56:1.

After xylene extraction of the H1 polymer, 60.6 wt % insoluble (H2) and39.4 wt % soluble (B3) polymer was recovered. The B2 insoluble fractionis subsequently measured to have 4.4 wt % C₂, Equations 2 thru 4 can besolved to account for this additional ethylene and result in 11.5 wt %EP soft polymer and 88.5 wt % iPP hard polymer.

Since the insoluble fraction contains 11.5 wt % EP copolymer, it shouldbe attached to an additional 7.35 wt % of iPP polymer based on theEP:iPP block ratio of 1.56:1. This brings the estimated amount ofdiblock in the insoluble fraction to be 29.6 wt %. For the entirepolymer (unfractionated), the composition is described as 18 wt % iPP-EPDiblock, 42.6 wt % iPP polymer, and 39.4 wt % EP polymer. For this H1example described above, the block composite index for the blockcomposite is 0.18. For the insoluble fraction (H2), the BCI is 0.29, andfor the H3 soluble fraction the BCI is assigned a value of zero.

Table 3 and FIG. 6 show the block composite indices for runs B1 throughABE For runs B1, C1, and D1, the BCI values are 0.16, 0.17, and 0.22,respectively. For the associated xylene insoluble fractions, fractionsB2, C2, D2, the BCI values are 0.42, 0.34, and, 0.35, respectively. Forruns F1, G1, and H1, the BCI values are 0.10, 0.15, and 0.18,respectively. For the associated xylene insoluble fractions, fractionsF2, G2, H2, the BCI values are 0.29, 0.29, and, 0.29, respectively.

Table 3 and FIG. 7 show for runs V1, W1, X1, increasing the propylenereactor conversion from 90 to 95% increases the BCI by 0.03 to 0.09 toresult in BCI values of 0.18, 0.24, and 0.25.

Table 3 and FIG. 7 show for runs Z1, AA1, AB1 increasing the reactortemperature from 90 to 120° C. resulted in BCI values of 0.12, 0.18, and0.24, respectively.

Dynamic Mechanical Analysis

FIG. 8 shows the dynamic mechanical properties of samples B1 through D1;shown is the G′ and Tan delta values versus temperature. By increasingthe amount of iPP, the G′ modulus increases and the high temperatureplateau is extended. Sample D1 shows that the modulus decreases withincreasing temperature up to about 140° C. before completely softeningafter its melting transition.

For each sample, the tan delta curve shows a characteristic Tg between−48 to −50° C. for the ethylene-propylene copolymer and a second Tg atabout 0° C. from the isotactic polypropylene. Above 50° C., the tandelta response remains constant until melting begins and the modulusdecreases rapidly.

FIG. 9 shows the dynamic mechanical properties of samples F1 through H1;shown are the G′ and Tan delta values versus temperature. Similar to the65 wt % C₂ case, by increasing the amount of iPP, the G′ modulusincreases and the high temperature plateau is extended. Sample H1 showsthat the modulus decreases with increasing temperature up to about 140°C. before completely softening after its melting transition.

The tan delta curves for these samples, also show a characteristic Tgbetween −48 to −50° C. for the ethylene-propylene copolymer and a secondTg about 0° C. relating to the isotactic polypropylene. Above 50° C.,the tan delta response remains constant for samples G1 & H1 untilmelting begins and the modulus decreases rapidly.

Morphology Discussion

The samples are analyzed by TEM to observe the influence of the diblockon the overall iPP/EPR rubber morphology. FIG. 10 shows the TEM image ofProFax Ultra SG853 impact copolymer (LyondellBasell Polyolefins)consisting of an isotactic PP continuous phase and 17 wt % rubber phase,containing 58 wt % C₂ in the rubber.

The TEM micrograph shown at the 5 μm scale, shows large EPR domainsranging from 2-5 μm.

At 1 μm magnification, the EPR domain has a heterogeneous compositiondistribution of ethylene and propylene as shown from the dark and lightcolored domains present within the particle. This is a classical exampleof a dispersed morphology containing two phases (iPP and EP rubber) thatare immiscible with each other.

FIG. 11 shows the TEM micrographs of compression molded films of B1, C1,and D1 at the 2, 1, and 0.5 μm scale. In stark contrast to the imagefrom the impact copolymer, all three polymers show a finer dispersion ofparticles with very small domains. For B1, a continuous EPR phase isobserved along with elongated PP domains on the order of 80-100 nm inwidth. For C1, a mixed continuity between the iPP and EPR phases wasobserved with domain sizes on the 200-250 nm. For D1, a PP continuousphase is observed along with spherical and some elongated EPR domains onthe size 150-300 nm.

FIG. 12 shows the TEM micrographs of compression molded films of F1, G1,and H1 at the 2, 1, and 0.5 μm scale. In stark contrast to the imagefrom the impact copolymer, all three polymers show a finer dispersion ofparticles with very small domains. For F1, a continuous EPR phase isobserved along with elongated PP domains on the order of 200-400 nm inwidth. For C1, a mixed continuity between the iPP and EPR phases wasobserved with domain sizes on the 200-300 nm. For H1, a PP continuousphase is observed along with spherical and some elongated EPR domains onthe size 150-300 nm.

It is surprising to observe such well-dispersed and small domains asshown in these micrographs from polymers that were compression moldedfrom pellets. Normally to get a fine morphology (not near the scalesshown here), specialized extrusion and compounding histories arerequired. Even if the size scales are approached using blending, themorphologies may not be stable; phase coarsening and agglomeration canoccur with the thermal aging, as shown by the impact copolymer in whichthe rubber domains are elongated and some of them chain-linked together.

The morphology of the diblock copolymer was further investigated byexamining the polymer fractions obtained from xylene fractionation. Asexplained above, the insoluble fraction contains iPP-EP diblock and freeiPP homopolymer while the soluble fraction contains, thenon-crystallizable EP rubber.

FIG. 13 shows the TEM micrographs of the insoluble fractions from B1 andD1 and also the soluble fraction from B1. Remarkably, the morphologyobserved in the insoluble fraction is even finer and more distinct thanthat of the whole polymer. The B1 insoluble fraction shows a mixture ofworm-like and spherical EPR domains, on the size-scale of 50 nm inwidth. The D1 insoluble fraction shows small spherical domains that arealso about 50 nm in diameter. For reference, the B1 xylene solublefraction shows the typical granular lamellar structure that is expectedof an EP elastomer containing 65 wt % C₂. Again, the morphologies of theinsoluble fractions are distinct and appear to be microphase separated.

It is interesting to compare the TEM micrographs of the B1 insolublefraction, FIG. 15, to that of an sPP-EP-sPP triblock containing 71 wt %sPP, such as that shown in FIG. 7 of Macromolecules, Vol. 38, No. 3,page 857, 2005. In this figure, the sPP-EP-sPP triblock was produced viaanionic polymerization and the micrograph is from a film annealed at160° C. for over one week. The sample was annealed in the melt for atotal of 8 days—the first 4 days at 200° C. to erase any previousthermal history and then an additional 4 days at a final temperature160° C. High-vacuum ovens (<10⁻⁷ mbar) were used to prevent degradationby oxidation. Melt morphology was preserved by quickly quenching thesamples after annealing. The authors of the article associate the phaseseparated microstructure to hexagonally packed cylinders. Although theB1 insoluble fraction is prepared from a compression molded film that isfast quenched, the morphology resembles that of an ordered structureperhaps with some hexagonally packed cylinders (FIG. 14).

TPV Formulations and Mechanical Properties

Raw Materials:

Raw materials are shown in Table 4. The NORDEL MG resin contains 28parts of carbon black per 100 parts EPDM elastomer. The carbon black isadhered to the resin in the form of core-shell morphology. Table 5 showsthe composition and physical characterisitics of all polymeringredients.

TABLE 4 Materials Chemical Name CAS Number Supplier DOW 5D49(38 MFR,9003-07-0 The Dow Chemical polypropylene homopolymer) Company PROFAX6823 (0.45MFR, 9003-07-0 Lyondell Basell polypropylene homopolymer)Polyolefins DOW H700-12 (12MFR, 9003-07-0 The Dow Chemical polypropylenehomopolymer) Company NORDEL MG 47130.01 25038-36-2 The Dow ChemicalCompany NORDEL IP 4570 25038-36-2 The Dow Chemical Company Blockcomposite / The Dow Chemical Company Sunpar ™ 150 64741-88-4 Sunoco Inc.Hydrobrite 550 (a 550 8042-47-5 Sonneborn. Inc cP clear aliphatic oilwith a refractive index of 1.4752) SP 1045 phenolic resin 26678-93-3 SIGroup Stannous chloride 10025-69-1 Mason Corporation curing catalystSunproof ™ 8002-74-2 Chemtura Improved (wax) Kadox ™ 720 1314-13-2 ZincCorporation (zinc oxide) of America Irganox 1076 2082-79-3 CibaSpecialty Chemicals Corporation Irganox B225 / Ciba Specialty ChemicalsCorporation

TABLE 5 Composition and material characteristics of polymer ingredientsDensity M_(w) Melt Index Crystallinity Comonomer (g/cm³) (kg/mol)M_(w)/M_(n) (g/10 min) (%) (mol %) NORDEL 47130 0.984 240 2.45 145Mooney 9 29 (ML1 + 4) NORDEL 4570 0.860 210 2.55  68 Mooney 1 45 (ML1 +4) ENGAGE ™ 8150 0.868 176 2.03 0.5 16 36 (2.16 kg/190° C.) B1 0.876 1232.2 3.8 / 45 (2.16 kg/190° C.) C1 0.878 128 2.1 1.6 / 34 (2.16 kg/190°C.) PROFAX 6823 0.906 / /  0.45 / / (2.16 kg/230° C.) DOW H700-12 0.90 // 12   / / (2.16 kg/230° C.) DOW 5D49 0.90 / / 38   / / (2.16 kg/230°C.)

TPV Example 1 Twin Screw Extruder Continuous TPV Process Using NORDEL MGas the Rubber Phase

Preparation Steps:

The process oil, EPDM resin, polypropylene powder, OBC resin, wax, andpowder additives are compounded in a Coperion 25-mm co-rotating twinscrew extruder (TSE). Part of the process oil is fed into the secondbarrel section using a positive displacement gear pump and an injectionvalve that minimizes backflow. The appropriate amount of melted SP 1045phenolic curing resin is added slowly to 3000 grams process oil at aminimum 90° C. temperature under agitation. Additional oil and thephenolic curing resin melted into additional process oil are injected inone barrel. All oil streams are preheated using a jacketed reservoir andheat-traced transfer lines. Low molecular weight volatile components areremoved by devolatilization ports. The material is then cooled andpelletized using a strand or underwater pelletizer at the end of theextruder.

The extruder has twelve-barrel sections, resulting in a totallength-to-diameter (L/D) ratio of 49. The feed system for this extrusionline has two loss-in-weight feeders. The NORDEL MG resin pellets, waxand 1 percent process oil are preblended in a plastic bag prior toadding into the main feed throat of the extruder using a K-Tron KCLQX3single-screw feeder. The powder additives are either fed alone orpremixed with polypropylene powder. The polypropylene powder is mixedwith all the other powder additives and tumble blended in a plastic bagprior to metering the material using a K-Tron KCLKT20 twin-screw powderfeeder.

The process oil is added to the extruder using a Leistritz Gear Pumpcart with two heat traced liquid feed systems.

A vacuum system is used to remove residual volatile components from themelt near the end of the extruder. Two knock-out pots in series arefilled with dry ice and isopropyl alcohol to condense the volatilecomponents. For compounded pellets, the polymer discharged from theextruder is cooled in a 10-foot long water bath, and cut into cylinderswith a Conair model 304 strand pelletizer. Discharge temperatures aremeasured using a hand-held thermocouple probe placed directly in themelt stream.

Formulations and Properties of NORDEL MG Examples:

TABLE 6 Ingredients Comparative Example Example (parts per hundred)Example T1 T4 T5 EPDM (NORDEL MG 47130) 128 121.6 121.6 PP 5D-49 50 5050 B1 7.5 C1 7.5 Sunpar 150 Oil 130 130 130 SP 1045 Phenolic Resin 3 3 3Stannous Chloride 1.7 1.7 1.7 (Dihydrate) Sunproof Improved (wax) 3 3 3Kadox 720 (zinc oxide) 2 2 2 Irganox 1076 1 1 1

Table 6 shows the formulations of TPV examples using NORDEL MG as therubber phase. The examples include a control example, Comparative T1,which is prepared without OBC compatibilizers, and two inventiveexamples, Examples T4 and T5, of TPV prepared with 5 wt % Examples B1and C1, based on total polymer base, as compatibilizers. Table 7 liststheir key mechanical properties. A comparison of Example T4 to ExampleT1 shows the addition of Example B1 resulted in a softer composition,with a significant decrease in the compression set at 70° C. and 120° C.while tensile strength was preserved. Example T5 had a similar hardness,tensile strength, elongation, and compression set at 70° C. relative toExample T1, but showed improved compression set at 120° C.

TABLE 7 Mechanical properties of TPV samples of the inventive andcomparative examples Comparative Example Example Properties Example T1T4 T5 Hardness (Shore A 10 sec) 64 59 63 Tensile Strength at break (psi)600 620 591 Elongation at break (%) 398 384 405 Compression Set 25%, 22hr at 48 38 47 70° C. (%) Compression Set 25%, 70 hr at 73 57 65 120° C.(%)

AFM phase images of Comparative Example T1 and Example T4 are shown inFIG. 15. The darker phase is cross-linked rubber particles, the lighterphases are polypropylene. The morphology of TPVs is typically across-linked rubber phase dispersed in a thermoplastic matrix. It may beseen that a finer morphology is achieved in the inventive example thanin the comparative example, which demonstrates better compatibilitybetween the EPDM and the PP phase.

TPV Example 2 Internal Mixer Batch TPV Process Using NORDEL IP as theRubber Phase

Preparation Steps:

The EPDM (NORDEL IP 4570) was imbibed with oil in a glass jar at 50° C.for at least 24 hours. The oil-imbibed EPDM elastomer, thermoplastic(Polypropylene)) and compatibilizer (OBC) were added to a Haake mixerbowl at 190° C. and 35 RPM. The materials were mixed for 4 minutes at 75rpm. The cure package (ZnO, SnCl2 and phenolic resin SP 1045) was addedto the molten mixture, and the mixing was allowed to continue for 3 moreminutes. The antioxidant was added, and the mixing was allowed tocontinue for one more minute. The melt was removed from the internalmixer, and allowed to further mix on a 2-roll mill at 190° C. The meltwas passed through the mixer and the resulting sheet was rolled into acigar-shaped specimen before being placed end-wise in to and passedthrough the mill. The procedure was repeated 6 times, and then thesample was taken off the mill as a sheet. The sheet from the mill waspreheated in a heated press (190° C.) for two minutes under 2000 psi ofpressure. Then the sheet was compression molded at 190° C. under 55000psi of pressure for 4 minutes and then cooled for 4 minutes with 55000psi of pressure. This procedure produced good test plaques with 1/16inch and ⅛ inch thickness without visible cracks.

Formulations and Properties of NORDEL IP Examples:

Table 8 shows the formulations of numerous TPV examples using NORDEL IPas the rubber phase. Hydrobrite 550 Oil was added at 75 pph, SP 1045phenolic resin was added at 3 pph, stannous chloride was added at 6 pph,Kadox 720 (zinc oxide) was added at 2 pph and Irganox 225 was added at 1pph to each formulation. The examples include two comparative examplesand 6 inventive examples of TPV prepared with Example B1 and C1 at threedifferent concentration levels. Example C11 was a control exampleprepared without any compatibilizer. Example C12 was a comparativeexample prepared with 6 wt % random ethylene/octene copolymer ascompatibilizer. Example C17 was prepared with 2 wt % of Example B1 on atotal polymer base. Example C09 was prepared with 6 wt % of Example B1on a total polymer base. Example C18 was prepared with 10 wt % ofExample B1 on a total polymer base. Example C06 was prepared with 2 wt %of Example C1 on a total polymer base. Example C08 was prepared with 6wt % of Example C1 on a total polymer base. Example C01 was preparedwith 10 wt % of Example C1 on a total polymer base.

TABLE 8 Ingredients Comparative Comparative Example Example ExampleExample Example Example (parts per hundred) Example C11 Example C12 C17C09 C18 C06 C08 C01 EPDM (Nordel IP 100 94 98 94 90 98 94 90 4570) PPDOW H700-12 50 47 49 47 45 49 47 45 ENGAGE 8150 9 B1 3 9 15 C1 3 9 15

Table 9 shows physical properties of the formulations given in Table 8.As can be seen, tear strength, tensile strength and ultimate elongationincreased for Comparative Example C12 and Inventive Examples C06, C08and C01. However, only the inventive examples show significantly lowercompression set, indicating better elastic recovery.

TABLE 9 Comparative Comparative Example Example Example Example ExampleExample Example C11 Example C12 C17 C09 C18 C06 C08 C01 Hardness 67 6664 68 65 68 68 66 (Shore A 10 sec) Tear Strength 155 172 159 164 155 173177 169 (lb/inch) Tensile Strength 506 767 769 682 750 663 812 849 atbreak (psi) Elongation 310 441 398 352 378 353 410 323 at break (%)Compression Set 59 50 40 43 26 46 37 35 25%, 22 hr at 70° C. (%)Compression Set 72 67 55 65 56 61 53 50 25%, 70 hr at 120° C. (%)

Table 10 shows another set of TPV examples using NORDEL IP as the rubberphase and a high molecular weight PP as the thermoplastic phase. Theexamples include a control example, which was prepared without OBCcompatibilizers, and 6 inventive examples of TPV prepared with ExampleB1 and C1 at three different levels. Example TM1 was a control exampleprepared without OBC compatibilizer. Example C04, C02 and C19 wereprepared with 2 wt %, 6 wt % and 10 wt % Example B1 on a total polymerbase, respectively. Examples C20, C16 and C05 were prepared with 2 wt %,6 wt % and 10 wt % Example B1 on a total polymer base, respectively.

TABLE 10 Formulations of inventive TPV examples and comparative TPVexamples Ingredients Comparative Example Example Example Example ExampleExample (parts per hundred) Example TM1 C04 C02 C19 C20 C16 C05 EPDM(Nordel IP 100 98 94 90 98 94 90 4570) PP PROFAX 50 49 47 45 49 47 456823 B1 3 9 15 C1 3 9 15

Hydrobrite 550 Oil was added at 75 pph, SP 1045 phenolic resin was addedat 3 pph, stannous chloride was added at 6 pph, Kadox 720 (zinc oxide)was added at 2 pph and Irganox 225 was added at 1 pph to eachformulation. Table 11 shows the mechanical properties of the TPVssamples. A comparison of the physical properties between Example C04 andcontrol Example TM1 shows by addition 2 wt % OBC, a stiffer TPV withdramatically higher elongation, higher tensile strength and lowercompression set were achieved. All other inventive Examples with OBCsshow the similar effect as Example C04 with improvement in everyproperty.

TABLE 11 Key mechanical properties of TPV samples of the inventive andcomparative examples Comparative Example Example Example Example ExampleExample Example TM1 C04 C02 C19 C20 C16 C05 Hardness 60 67 68 68 67 6368 (Shore A 10 sec) Tensile Strength 424 978 834 757 819 773 934 atbreak (psi) Elongation 285 391 393 350 387 438 389 at break %Compression Set 55 35 43 41 34 43 35 25%, 22 hr at 70° C. (%)Compression Set 79 51 58 58 50 58 49 25%, 70 hr at 120° C. (%)

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. Finally, any number disclosed herein should beconstrued to mean approximate, regardless of whether the word “about” or“approximately” is used in describing the number. The appended claimsintend to cover all those modifications and variations as falling withinthe scope of the invention.

We claim:
 1. A thermoplastic vulcanizate composition obtained from areaction mixture comprising: a) a vulcanizable elastomer; b) athermoplastic polyolefin; c) a cross-linking agent; and, d) a blockcomposite, wherein the thermoplastic vulcanizate has a reduction incompression set at 70° C. of greater than 5% as compared to thethermoplastic vulcanizate without (d) wherein the block compositecomprises a soft copolymer, a hard polymer and a block copolymer havinga soft segment and a hard segment, wherein the hard segment of the blockcopolymer is the same composition as the hard polymer in the blockcomposite and the soft segment of the block copolymer is the samecomposition as the soft copolymer of the block composite and the hardsegment comprises 80 wt% to 100 wt% propylene.
 2. The composition ofclaim 1 wherein (d) has a Block Composite Index ≧0.10.
 3. Thecomposition of claim 1 wherein the block composite comprises diblockcopolymers having isotactic polypropylene blocks and ethylene-propyleneblocks.
 4. The composition of claim 3 wherein the isotacticpolypropylene blocks are present in an amount of 10 wt% to 90 wt%. 5.The composition of claim 3 wherein the ethylene content of theethylene-propylene blocks is 35 wt% to 70 wt%.
 6. The composition ofclaim 1 wherein the block composite is present in an amount of 1 wt % to30 wt %.
 7. The composition of claim 1 wherein the melt flow rate of theblock composite, measured at 230 ° C. and 2.16 kg weight, is 0.1 dg/minto 50 dg/min.
 8. The composition of claim 1 wherein the vulcanizableelastomer is selected from the group consisting of EPDM,ethylene/α-olefins, olefin block copolymers and block composites.
 9. Thecomposition of claim 1 wherein the thermoplastic polyolefin is selectedfrom the group consisting of polyethylene, polypropylene homopolymers,polypropylene copolymers and block composites.
 10. An article comprisingthe composition of claim 1.